Flame-retardant thermoplastic polyester resin composition and molded article
12 claims: 1 independent, 11 dependent
- 1(A)熱可塑性ポリエステル樹脂50~95重量部と(B) メタクリル酸エステルの残基を50重量%以上含有する メタクリル樹脂5~50重量部との合計100重量部に対し、(C-1)縮合リン酸エステル、(C-2)ホスファゼン化合物および(C-3)有機ホスフィン酸金属塩からなる群より選ばれた2種以上の(C)リン系難燃剤1~70重量部および(D)窒素系難燃剤1~90重量部を含有する難燃性熱可塑性ポリエステル樹脂組成物。
- 2(A)熱可塑性ポリエステルの含有量が70~90重量部であり、そして(B)メタクリル樹脂の含有量が10~30重量部である請求項1記載の難燃性熱可塑性ポリエステル樹脂組成物。
- 3(C)リン系難燃剤が、(C-1)縮合リン酸エステルおよび(C-2)ホスファゼン化合物を含有する請求項1または2記載の難燃性熱可塑性ポリエステル樹脂組成物。
- 4(C-1)縮合リン酸エステルと(C-2)ホスファゼン化合物の含有量比が、(C-1)縮合リン酸エステルと(C-2)ホスファゼン化合物の合計100重量%に対して、(C-1)縮合リン酸エステルが30~70重量%であり、(C-2)ホスファゼン化合物が70~30重量%である請求項3記載の難燃性熱可塑性ポリエステル樹脂組成物。
- 5さらに、(A)熱可塑性ポリエステル樹脂と(B)メタクリル樹脂との合計100重量部に対し、(E)芳香族ポリカーボネート樹脂1~50重量部を含有する請求項1~4のいずれかに記載の難燃性熱可塑性ポリエステル樹脂組成物。
- 6(B)メタクリル樹脂と(E)芳香族ポリカーボネート樹脂の合計含有量に対する、(C-1)縮合リン酸エステルおよび(C-2)ホスファゼン化合物の合計含有量の比({(C-1)+(C-2)}/{(B)+(E)})が、50/50~30/70(重量比)である請求項5記載の難燃性熱可塑性ポリエステル樹脂組成物。
- 7さらに、(A)熱可塑性ポリエステル樹脂と(B)メタクリル樹脂との合計100重量部に対し、(F)アルカリ土類金属塩0.01~5重量部を含有する請求項1~6のいずれかに記載の難燃性熱可塑性ポリエステル樹脂組成物。
- 8(F)アルカリ土類金属塩が、炭酸カルシウムである請求項7記載の難燃性熱可塑性ポリエステル樹脂組成物。
- 9さらに、(A)熱可塑性ポリエステル樹脂と(B)メタクリル樹脂との合計100重量部に対し、(G)ガラス繊維1~150重量部を含有する請求項1~8のいずれかに記載の難燃性熱可塑性ポリエステル樹脂組成物。
- 10請求項1~9のいずれかに記載の難燃性熱可塑性ポリエステル樹脂組成物を溶融成形し た 成形品。
- 11IEC60112に準拠した比較トラッキング指数が400V以上である請求項10記載の成形品。
- 12燃焼時にリン系難燃剤由来の層が表層から20nm以上形成され た 請求項10または11記載の成形品。
Independent claims12
175 paragraphs, as filed
The present invention relates to a flame-retardant thermoplastic polyester resin composition and a molded product obtained by molding the composition. In particular, the present invention relates to a flame-retardant thermoplastic polyester resin composition in which the tracking resistance of a molded product is improved by containing a specific amount of methacrylic resin, and a molded product obtained by molding the composition. ..
Thermoplastic polyester resins are used in a wide range of fields such as mechanical mechanical parts, electrical / electronic parts, and automobile parts by taking advantage of their excellent injection moldability and mechanical physical characteristics.
However, because thermoplastic polyester resins are flammable in nature, they have general chemical and physical properties for use as industrial materials such as mechanical components, electrical and electronic components and automotive components. In addition to the balance of flames, safety against flames, that is, flame retardancy is required, and in many cases, high flame retardancy indicating V-0 of UL-94 standard is required. In addition, when used in an environment where electricity flows, safety against tracking destruction ignited by decomposition or carbonization of resin due to electric discharge, that is, tracking resistance, is required, and advanced tracking resistance indicating CTI rank 0 of the IEC60112 standard is required. Sex is often required. In particular, in recent years, electric vehicles have been attracting attention due to heightened environmental awareness, and even higher tracking resistance is required.
As a method for imparting tracking resistance to a thermoplastic polyester resin, a method of incorporating an electrical property improving agent such as an organic phosphinic acid compound or melamine cyanurate is generally used.
As a method for improving flame retardancy and electrical properties of a thermoplastic polyester resin, for example, a polyalkylene terephthalate resin, a vinyl resin, a phosphoric acid ester, and a triazine compound and a salt of cyanuric acid or isocyanuric acid are used. A constructed flame-retardant resin composition having improved electrical characteristics has been proposed (see Patent Document 1). However, this proposal has the problem that flame retardancy and electrical characteristics are still insufficient.
In addition, as other methods for improving flame retardancy and electrical properties, for example, a base resin and an electrical property improving aid such as a halogen-based flame retardant, an organic phosphinic acid or a salt thereof, a flame retardant aid, and melamine cyanurate. A flame-retardant resin composition having improved electrical characteristics has been proposed (see Patent Document 2). However, this proposal has a problem that the tracking resistance is still insufficient. Further, since a resin composition containing a halogen-based flame retardant may generate harmful dioxins during combustion, a flame-retardant resin composition using a non-halogen flame retardant is required.
Examples of the flame-retardant resin composition using a non-halogen flame retardant include a resin composition obtained by blending a thermoplastic resin such as a polybutylene terephthalate resin, a phosphoric acid ester compound, and a methacrylic resin (see Patent Document 3). .), Thermoplastic resins such as polybutylene terephthalate resin and methacrylic resin, phosphoric acid ester flame retardants, at least one metal salt selected from alkali metal salts and alkaline earth metal salts, and triazine compounds and cyanur. A resin composition containing a salt with an acid or isocyanuric acid (see Patent Document 4) has been proposed. Further, as a flame retardant resin composition that uses a non-halogen flame retardant and has both mechanical properties and flame retardancy, for example, a thermoplastic polyester resin, a phosphazene flame retardant, a phosphoric acid ester flame retardant, and melamine. A phosphorus-based resin composition containing a nitrogen compound such as a cyanuric acid adduct (see Patent Document 5), a thermoplastic polyester resin, a specific aromatic phosphoric acid ester compound, and a phosphoric acid ester compound having a molecular weight of 100 to 500. A resin composition (see Patent Document 6) containing a flame retardant and a flame retardant such as a nitrogen compound flame retardant has been proposed. However, although the resin compositions described in Patent Documents 3 and 4 can improve the low warpage property of the molded product, there is a problem in tracking resistance. Further, the resin compositions described in Patent Documents 5 and 6 also have a problem that the tracking resistance is insufficient.
<p num="0008"><patcit num="1"><text>Japanese Patent Application Laid-Open No. 2002-294051</text></patcit><patcit num="2"><text>International Publication No. 2006/090751</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 2009-96969</text></patcit><patcit num="4"><text>Japanese Unexamined Patent Publication No. 2008-169363</text></patcit><patcit num="5"><text>Japanese Unexamined Patent Publication No. 2011-231150</text></patcit><patcit num="6"><text>Japanese Unexamined Patent Publication No. 2010-6965</text></patcit></p>
<p num="0009"> The thermoplastic polyester resin is decomposed by electric discharge or the like, and carbonized carbide remains on the resin surface, so that it becomes a conductive substance and the tracking resistance is lowered. As a method for improving the tracking resistance of thermoplastic polyester resin, a structure such as a benzene ring contained in the resin structure, which is incompletely burned because high energy is required for complete combustion and easily leaves carbides on the resin surface, is used. There are methods that contain less resin. However, since a resin having no structure such as a benzene ring is generally inferior in flame retardancy, the flame retardancy of the entire resin composition tends to be lowered by containing such a resin. Further, although the flame retardancy can be improved by containing a large amount of the non-halogen flame retardant, there is a problem that the mechanical properties are deteriorated.</p><p num="0010"> Therefore, an object of the present invention is to provide a flame-retardant thermoplastic polyester resin composition having excellent tracking resistance and mechanical properties of a molded product while maintaining a high degree of flame retardancy, and a molded product obtained by molding the composition. It is in.</p>
<p num="0011"> As a result of repeated studies to solve the above-mentioned problems, the present inventors have made (A) a thermoplastic polyester resin contain a specific amount of (B) methacrylic resin, and further (C-1) a condensed phosphoric acid ester. , (C-2) Phosphazene compound and (C-3) Two or more phosphorus-based flame retardants selected from the group consisting of organic phosphinic acid metal salts and (D) Nitrogen-based flame retardants shall be contained in specific amounts. As a result, it was found that the above-mentioned problems could be solved, and the present invention was reached.</p><p num="0012"> The present invention is intended to solve the above-mentioned problems, and the flame-retardant thermoplastic polyester resin composition of the present invention comprises (A) 50 to 95 parts by weight of the thermoplastic polyester resin and (B).<u style="single">Contains 50% by weight or more of a methacrylic acid ester residue</u>Selected from the group consisting of (C-1) condensed phosphoric acid ester, (C-2) phosphazene compound and (C-3) organic phosphinic acid metal salt with respect to 100 parts by weight in total including 5 to 50 parts by weight of methacrylic resin. It is a flame-retardant thermoplastic polyester resin composition containing 1 to 70 parts by weight of (C) phosphorus-based flame retardant and 1 to 90 parts by weight of (D) nitrogen-based flame retardant.</p><p num="0013"> According to a preferred embodiment of the flame-retardant thermoplastic polyester resin composition of the present invention, the content of the (A) thermoplastic polyester is 70 to 90 parts by weight, and the content of the (B) methacrylic resin is described. Is 10 to 30 parts by weight.</p><p num="0014"> According to a preferred embodiment of the flame-retardant thermoplastic polyester resin composition of the present invention, the (C) phosphorus-based flame retardant contains (C-1) condensed phosphoric acid ester and (C-2) phosphazene compound. It is to be.</p><p num="0015"> According to a preferred embodiment of the flame-retardant thermoplastic polyester resin composition of the present invention, the content ratio of the (C-1) condensed phosphoric acid ester to the (C-2) phosphazene compound is (C-1) condensed. The (C-1) condensed phosphoric acid ester is 30 to 70% by weight and the (C-2) phosphazene compound is 70 to 30% by weight based on 100% by weight of the total of the phosphoric acid ester and the (C-2) phosphazene compound. %.</p><p num="0016"> According to a preferred embodiment of the flame-retardant thermoplastic polyester resin composition of the present invention, (E) aromatics are further based on 100 parts by weight of the total of the (A) thermoplastic polyester resin and (B) methacrylic resin. It contains 1 to 50 parts by weight of a polycarbonate resin.</p><p num="0017"> According to a preferred embodiment of the flame-retardant thermoplastic polyester resin composition of the present invention, the above (C-1) condensation with respect to the total content of the above (B) methacrylic resin and the above (E) aromatic polycarbonate resin. The total content ratio ({(C-1) + (C-2)} / {(B) + (E)}) of the phosphoric acid ester and the above-mentioned (C-2) phosphazene compound is 50/50 to 30. / 70 (weight ratio).</p><p num="0018"> According to a preferred embodiment of the flame-retardant thermoplastic polyester resin composition of the present invention, (F) alkaline earth metal is further based on 100 parts by weight of the total of (A) thermoplastic polyester resin and (B) methacrylic resin. It is to contain 0.01 to 5 parts by weight of salt.</p><p num="0019"> According to a preferred embodiment of the flame-retardant thermoplastic polyester resin composition of the present invention, the (F) alkaline earth metal salt is calcium carbonate.</p><p num="0020"> According to a preferred embodiment of the flame-retardant thermoplastic polyester resin composition of the present invention, (G) is further based on 100 parts by weight of the total of the (A) thermoplastic polyester resin and the (B) methacrylic resin. It contains 1 to 150 parts by weight of glass fiber.</p><p num="0021"> The flame-retardant thermoplastic polyester resin composition of the present invention is melt-molded.<u style="single">Ta</u>It can be a molded product.</p><p num="0022"> According to a preferred embodiment of the article of the present invention, the article has a comparative tracking index of 400 V or greater according to IEC60112.</p><p num="0023"> According to a preferred embodiment of the molded product of the present invention, a phosphorus-based flame retardant-derived layer is formed at 20 nm or more from the surface layer when the molded product is burned.<u style="single">Ta</u>That is.</p>
<p num="0024"> According to the present invention, it is possible to obtain a flame-retardant thermoplastic polyester resin composition having an excellent balance between tracking resistance and mechanical properties of a molded product while maintaining a high degree of flame retardancy, and a molded product obtained by molding the composition. Can be done. The molded product made of the flame-retardant thermoplastic polyester resin composition of the present invention is useful as a molded product such as mechanical mechanical parts, electrical / electronic parts, and automobile parts.</p>
Next, the flame-retardant thermoplastic polyester resin composition of the present invention will be described in detail.
The flame-retardant thermoplastic polyester resin composition of the present invention has (C-1) with respect to a total of 100 parts by weight of (A) 50 to 95 parts by weight of thermoplastic polyester resin and (B) 5 to 50 parts by weight of methacrylic resin. ) Condensed phosphoric acid ester, (C-2) Phosphazenic compound and (C-3) Organic phosphinic acid metal salt Two or more kinds selected from the group consisting of 1 to 70 parts by weight of (C) phosphorus flame retardant and (D) Contains 1 to 90 parts by weight of a nitrogen-based flame retardant.
The (A) thermoplastic polyester resin used in the present invention includes (a) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, and (c). ) A polymer or copolymer having one or more residues selected from lactone as the main structural unit. Here, the main structural unit means having 50 mol% or more of one or more residues selected from (a) to (c) in all the structural units, and it is preferable to have 80 mol% or more. is there.
Examples of the above-mentioned dicarboxylic acid or its ester-forming derivative include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, and anthracene dicarboxylic acid. , 4,4'-Diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid and other aromatic dicarboxylic acids, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecandic acid, Examples thereof include aliphatic dicarboxylic acids such as malonic acid, glutaric acid and dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.
Examples of the above diols or ester-forming derivatives thereof include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, and cyclohexane. Long chain glycols with a molecular weight of 200 to 100,000 such as aliphatic glycols having 2 to 20 carbon atoms such as dimethanol, cyclohexanediol and dimerdiol, polyethylene glycols, poly-1,3-propylene glycols and polytetramethylene glycols, 4,4 Aromatic dioxy compounds such as'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and ester-forming derivatives thereof can be mentioned.
Interphthalate / succinate, polybutylene terephthalate / succinate, polyethylene terephthalate / adipate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polyethylene terephthalate / sevacate, polypropylene terephthalate / sebacate, polybutylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / adipate , Polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate and other aromatic polyester resins, polyethylene oxalate, polypropylene oxalate, Polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene succinate Examples include aliphatic polyester resins such as / adipate, polypropylene succinate / adipate, and polybutylene succinate / adipate. Here, "/" represents a copolymer. Aromatic polyester resins such as polybutylene terephthalate / isophthalate / sebacate, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate , Polyneopentyl glycol adipate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, and aliphatic polyester resins such as polybutylene succinate / adipate. Here, "/" represents a copolymer. Aromatic polyester resins such as polybutylene terephthalate / isophthalate / sebacate, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate , Polyneopentyl glycol adipate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, and aliphatic polyester resins such as polybutylene succinate / adipate. Here, "/" represents a copolymer.
Examples of the hydroxycarboxylic acid or an ester-forming derivative thereof include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, and 6-hydroxy-2. -Naftoeic acid, and ester-forming derivatives thereof and the like. Examples of the polymer or copolymer having these as structural units include aliphatic polyester resins such as polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, and polyhydroxybutyric acid / β-hydroxybutyric acid / β-hydroxyvaleric acid. And so on.
Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone and 1,5-oxepane-2-one. Examples of the polymer or copolymer having these as structural units include polycaprolactone, polyvalerolactone, polypropiolactone and polycaprolactone / valerolactone.
Among these, as the above-mentioned (A) thermoplastic polyester resin, a polymer or copolymer having a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as a main structural unit is preferable, and an aromatic dicarboxylic acid is preferable. Alternatively, a polymer or copolymer having the ester-forming derivative and the aliphatic diol or the ester-forming derivative as the main structural unit is more preferable, and terephthalic acid, naphthalenedicarboxylic acid or the ester-forming derivative thereof and ethylene glycol or propylene glycol are more preferable. , Butanediol, an aliphatic diol selected from cyclohexanedimethanol, or a polymer or copolymer having an ester-forming derivative thereof as a main structural unit is more preferable.
Among them, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, Aromatic polyester resins such as polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, and polybutylene terephthalate / naphthalate are particularly preferred, with polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethylene terephthalate being most preferred. In addition, two or more of these can be used in any content.
In the present invention, the ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer or copolymer having the above-mentioned dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as a main structural unit. Is preferably 30 mol% or more, more preferably 40 mol% or more.
In the present invention, as the (A) thermoplastic polyester resin, a liquid crystal polyester that can form anisotropy when melted can be used. Structural units of the liquid crystal polyester include aromatic oxycarbonyl units, aromatic dioxy units, aromatic and / or aliphatic dicarbonyl units, alkylenedioxy units, aromatic iminooxy units and the like.
The amount of carboxyl terminal groups of the (A) thermoplastic polyester resin used in the present invention is preferably 50 eq / t or less, more preferably 30 eq / t or less in terms of fluidity, hydrolysis resistance and heat resistance. It is more preferably 20 eq / t or less, and particularly preferably 10 eq / t or less. The lower limit of the amount of carboxyl terminal groups is about 0eq / t. Here, the amount of the carboxyl terminal group of the (A) thermoplastic polyester resin is a value measured by dissolving it in an o-cresol / chloroform solvent and then titrating it with ethanolic potassium hydroxide.
The amount of hydroxy terminal groups of the (A) thermoplastic polyester resin used in the present invention is preferably 50 eq / t or more, more preferably 80 eq / t or more, still more preferably 80 eq / t or more, in terms of moldability and fluidity. Is 100 eq / t or more, and particularly preferably 120 eq / t or more. The upper limit of the amount of hydroxy end groups is 180 eq / t.
The viscosity of the (A) thermoplastic polyester resin of the present invention is such that the intrinsic viscosity of the o-chlorophenol solution measured at a temperature of 25 ° C is in the range of 0.50 to 1.50 dl / g in terms of moldability. Is preferable.
The molecular weight of the (A) thermoplastic polyester resin used in the present invention is preferably in the range of more than the weight average molecular weight (Mw) of 8000 and not more than 500,000, more preferably more than 8,000 and not more than 300,000 in terms of heat resistance. It is a range, more preferably a range of more than 8000 and less than 250,000. In the present invention, (A) Mw of the thermoplastic polyester resin is a value converted to polymethylmethacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
The (A) thermoplastic polyester resin in the present invention can be produced by a known polycondensation method, ring-opening polymerization method, or the like. The production method may be either batch polymerization or continuous polymerization, and can be applied to either a transesterification reaction or a reaction by direct polymerization, but the amount of carboxyl terminal groups can be reduced and the fluidity is improved. Continuous polymerization is preferable in terms of increasing the effect, and direct polymerization is preferably used in terms of cost.
When the (A) thermoplastic polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction containing a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as main components. Can be produced by subjecting a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof to an esterification reaction or an ester exchange reaction, and then a polycondensation reaction.
In order to effectively proceed with the esterification reaction or the transesterification reaction and the polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester of titanium acid, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, and phenyl ester. Organic titanium compounds such as benzyl esters, trill esters, or mixed esters of these, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethyldistin oxide, cyclohexahexyl distin oxide, didodecyltin oxide, triethyltin hydrooxide. , Triphenyltin Hydrooxide, Triisobutyltin Acetate, Dibutyltin Diacetate, Diphenyltin Dilaurate, Monobutyltin Trichloride, Dibutyltin Dichloride, Tributyltin Chloride, Dibutyltin Sulfide, Butylhydroxytin Oxide, Methylstannoic Acid, Ethylstannoic Acid, Butylstan Examples thereof include tin compounds such as alkylstan nonic acid such as non-acids, zirconia compounds such as zirconium tetra-n-butoxide, antimony compounds such as antimony trioxide, and antimony compounds such as antimony acetate.
Among these polymerization reaction catalysts, an organic titanium compound and a tin compound are preferable, further, a tetra-n-propyl ester of a titanium acid, a tetra-n-butyl ester and a tetraisopropyl ester are preferable, and a tetra-n-butyl of a titanoic acid is preferable. Esters are particularly preferably used. In the present invention, two or more of these polymerization reaction catalysts can be used in combination. The amount of the polymerization reaction catalyst added is preferably in the range of 0.005 to 0.5 parts by weight, more preferably in the range of 0.01 to 0.2 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin in terms of mechanical properties, moldability and color tone. Is.
In the present invention, the inclusion of the (B) methacrylic resin improves the tracking resistance, which is one of the electrical characteristics. In addition, by containing the component (B), it also has the effect of suppressing the bleed-out of the (C) phosphorus-based flame retardant. In particular, the component (C) contains the (C-1) condensed phosphate ester and (C-2). ) It has a remarkable effect on suppressing bleed-out when it is a phosphazene compound.
The (B) methacrylic resin in the present invention is a polymer having a residue of methacrylic acid ester as a main structural unit, and may be, for example, a copolymer of methacrylic acid ester such as polymethylmethacrylate, or methacrylic acid. It may be a copolymer of 50% by weight or more of ester and 50% by weight or less of other monomers. Here, the main structural unit means having 50% by weight or more of the residue of the methacrylic acid ester, preferably 70% by weight or more, and more preferably 90% by weight or more. In the present invention, two or more kinds of (B) methacrylic acid ester may be contained.
As the methacrylic acid ester, an alkyl methacrylate is preferable, and an ester having an alkyl group having 1 to 4 carbon atoms is more preferable. Among the esters having an alkyl group having 1 to 4 carbon atoms, methyl methacrylate is particularly preferably used. The above-mentioned methacrylic acid ester may be only one kind or two or more kinds.
Examples of the monomer other than the methacrylic acid ester include acrylic acid esters such as methyl acrylate and ethyl acrylate, aromatic alkenyl compounds such as styrene and α-methylstyrene, and unsaturateds such as acrylic acid and methacrylic acid. Examples thereof include carboxylic acids and alkenyl cyan compounds such as acrylonitrile and methacrylic acid. Among them, acrylate ester is preferable, and methyl acrylate is more preferably used.
As a polymerization method for polymerizing the above-mentioned monomer components, for example, known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be adopted. A chain transfer agent or a radical polymerization initiator is usually used for the polymerization. As the chain transfer agent, for example, mercaptans such as dodecyl mercaptan and octyl mercaptan are preferably used, and as the radical polymerization initiator, for example, an organic peroxide or an azo compound is preferably used.
The weight average molecular weight (Mw) of the (B) methacrylic resin used in the present invention is preferably 50,000 or more, more preferably 80,000 or more in terms of excellent flame retardancy, mechanical properties and bleed-out suppression. .. The weight average molecular weight (Mw) is preferably 300,000 or less, more preferably 200,000 or less, in terms of excellent fluidity. The Mw of the (B) methacrylic resin used in the present invention is a value converted to polymethylmethacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
The melt flow rate (MFR) of the (B) methacrylic resin used in the present invention is preferably 0.1 g / 10 minutes or more, more preferably 0.5 g / 10 minutes or more, in terms of fluidity. More preferably, it is 1 g / 10 minutes or more. The melt flow rate (MFR) is preferably 40 g / 10 minutes or less, more preferably 30 g / 10 minutes or less, still more preferably 20 g / 10 minutes, in terms of excellent mechanical properties and bleed-out. Less than a minute.
The MFR referred to here is a value measured according to the method described in ASTM D1238-04, and is a value measured at a temperature of 230 ° C and a load of 37.2 N.
The (B) methacrylic resin used in the present invention preferably has a glass transition temperature of 90 ° C or higher, more preferably 100 ° C or higher, and even more preferably 110 ° C or higher in terms of heat resistance. is there. The upper limit of the glass transition temperature is preferably a temperature of 150 ° C. or lower in terms of fluidity.
The glass transition temperature referred to here is a value measured according to the method described in JIS K 7121: 1987, and is an intermediate point glass transition temperature when the temperature is raised at 20 ° C / min by DSC measurement.
The (B) methacrylic resin used in the present invention preferably has a syndiotacticity of 40% or more, more preferably 45% or more, in terms of excellent mechanical properties and bleed-out suppression. On the other hand, in terms of fluidity, the syndiotacticity is preferably 90% or less, more preferably 80% or less.
Further, the heterotacticity of the (B) methacrylic resin is preferably 45% or less, more preferably 40% or less, in terms of excellent tracking resistance, mechanical properties and bleed-out suppression. The lower limit of heterotacticity is preferably 20% or more, more preferably 30% or more.
The isotacticity of (B) methacrylic resin is preferably 20% or less, more preferably 15% or less, in terms of excellent mechanical properties and bleed-out suppression. The lower limit of isotacticity is preferably 5% or more, more preferably 8% or more, still more preferably 10% or more.
Deuterated chloroform was used as a solvent for the stereoregularity of syndiotacticity, heterotacticity and isotacticity referred to here.<sup>1</sup>Assuming that the sum of the integrated intensities of the methyl group peaks of 0.9ppm, 1.0ppm, and 1.2ppm observed as syndiotacticity, heterotacticity, and isotacticity in 1 H-NMR measurement is 100%. , Can be calculated by expressing the ratio of the integrated intensity of each peak as a percentage.
In the present invention, the contents of (A) thermoplastic polyester resin and (B) methacrylic resin are 100 in total of (A) component and (B) component from the viewpoint of balance of flame retardancy, tracking resistance and heat resistance. The component (A) is 50 to 95 parts by weight and the component (B) is 5 to 50 parts by weight with respect to the parts by weight. When the content of the component (A) is less than 50 parts by weight and the content of the component (B) exceeds 50 parts by weight, the flame retardancy is lowered. In particular, in terms of flame retardancy, mechanical properties, fluidity and heat resistance, the content of component (A) is preferably 60 parts by weight or more, more preferably 65 parts by weight or more, and particularly preferably 70 parts by weight or more. Is. From the viewpoint of flame retardancy, mechanical properties, fluidity and heat resistance, the content of the component (B) is preferably 40 parts by weight or less, more preferably 35 parts by weight or less, and particularly preferably 30 parts by weight. It is as follows.
On the other hand, when the content of the component (A) exceeds 95 parts by weight and the content of the component (B) is less than 5 parts by weight, the tracking resistance and the bleed-out suppressing effect of the component (C) are lowered. The content of the component (A) is preferably 90 parts by weight or less in terms of tracking resistance, fluidity, heat resistance and bleed-out suppressing effect. The content of the component (B) is preferably 10 parts by weight or more because it is excellent in tracking resistance and bleed-out suppressing effect.
The (C) phosphorus-based flame retardant used in the present invention is two kinds selected from the group consisting of (C-1) condensed phosphate ester, (C-2) phosphazene compound and (C-3) organic phosphinic acid metal salt. It is a phosphorus-based flame retardant composed of the above phosphorus-containing compounds. By containing the component (C), flame retardancy can be improved, and by combining two or more phosphorus-based flame retardants selected from the above group, flame retardancy, fluidity and toughness are further improved.
Further, as the combination of the component (C), the combination of (C-1) and (C-3) can improve the flame retardancy while maintaining particularly high mechanical properties. Also, from the viewpoint of flame retardancy, mechanical properties, productivity and cost, (C-1) and (C-1), (C-1) and (C-2), (C-1) and (C- The combination selected from any of 3) is preferable, and the combination of (C-1) and (C-2) is more preferable from the viewpoint of the balance of electrical characteristics, flame retardancy and mechanical characteristics. By combining (C-1) and (C-2), the thickness of the flame retardant layer formed on the surface layer of the molded product during combustion becomes thicker, and in particular, the flame retardancy can be greatly improved.
Examples of the (C-1) condensed phosphate ester in the present invention include resorcinol phosphates (resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dixylenyl phosphate), hydroquinone bis (diphenyl phosphate). )), Hydroquinone phosphates (hydroquinone bis (dicresil phosphate), hydroquinone bis (dixylenyl phosphate)), biphenol phosphates (biphenol bis (diphenyl phosphate), biphenol bis (dicresil phosphate), biphenol bis (dixylenyl phosphate)) Phosphate)), bisphenol phosphates (bisphenol-A bis (diphenyl phosphate), bisphenol-A bis (dicresyl phosphate), and bisphenol-A bis (dixylenyl phosphate)) and the like. Two or more of these may be contained.
Commercially available products of (C-1) condensed phosphate ester include PX-202, CR-741, PX-200, PX-201 manufactured by Daihachi Chemical Industry Co., Ltd., and FP-500, FP manufactured by ADEKA Corporation. -600, FP-700, FP-800, PFR, etc. can be mentioned.
(C) When a combination of (C-1) and (C-1) is used as the phosphorus-based flame retardant, a combination of resorcinol phosphates and biphenol phosphates is preferably used from the viewpoint of further improving flame retardancy. Examples of commercially available resorcinol phosphates include PX-200 manufactured by Daihachi Chemical Industry Co., Ltd., and examples of commercially available biphenol phosphates include FP-800 manufactured by ADEKA Corporation.
The (C-2) phosphazene compound used in the present invention may be any compound having a -P = N- bond in the molecule, and is, for example, a chain or cyclic compound having a structure represented by the following general formula (1). Phosphazene compounds can be mentioned.
<chemistry num="1"><img id="000002" he="35" wi="58" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
(In the above general formula (1), n represents an integer from 1 to 1000.<sup>1</sup>And R<sup>2</sup>Are independently hydrogen atoms, linear, branched or cyclic alkyl groups with 1 to 18 carbon atoms, linear, branched or cyclic alkoxyl groups with 1 to 30 carbon atoms, and 6 carbon atoms. Represents an aryl group of 30 or more or an aryloxy group having 6 or more carbon atoms and 30 or less carbon atoms. ) In the above general formula (1), examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkoxyl group include a methoxy group and an ethoxy group. Examples of the aryl group include a phenyl group and the like. Examples of the aryloxy group include a phenyloxy group. n is preferably 3 to 30, and a cyclic phosphazene compound in which the structure represented by the above general formula (1) is cyclically bonded is preferable.
Further, the (C-2) phosphazene compound may be a crosslinked phosphazene compound crosslinked with a crosslinking group. Such a cross-linked phosphazene compound can be obtained, for example, by cross-linking a chain or cyclic phosphazene compound represented by the above general formula (1) with a divalent cross-linking group. Examples of the divalent bridging group include a phenylene group (o-phenylene group, m-phenylene group, p-phenylene group), and a bisphenylene group represented by the following general formula (2). The above-mentioned cross-linking groups can be used alone or in combination of two or more.
<chemistry num="2"><img id="000003" he="20" wi="89" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
(In general formula (2), A is -C (CH)<sub>3</sub>)<sub>2</sub>-,-SO<sub>2</sub>Represents-, -S- or -O-. a represents 0 or 1. ) As the (C-2) phosphazene compound, a synthesized compound may be used, or a commercially available product may be used. For the method of synthesizing phosphazene compounds, refer to the author Kajiwara, "Synthesis and Application of Phosphazene Compounds". Examples of commercially available products include crosslinked phosphazene compounds such as SPS-100, SPB-100, and SPE-100 manufactured by Otsuka Chemical Co., Ltd.
Examples of the (C-3) organic phosphinic acid metal salt used in the present invention include a metal salt of phosphinic acid represented by the following general formula (3) and a metal salt of diphosphanic acid represented by the general formula (4). Can be mentioned.
<chemistry num="3"><img id="000004" he="34" wi="64" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
(In general formula (3), R<sup>3</sup>And R<sup>4</sup>Independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms. M is calcium, aluminum or zinc. Also, m is an integer from 1 to 4. )
<chemistry num="4"><img id="000005" he="34" wi="95" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
(In general formula (4), R<sup>3</sup>And R<sup>4</sup>Independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R<sup>5</sup>Represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms. M is calcium, aluminum or zinc. Also, m is an integer from 1 to 4. ) Examples of commercially available products of the (C-3) organic phosphinic acid metal salt include "Exolit" (registered trademark) OP1230 and OP1240 manufactured by Clariant Japan Co., Ltd. In addition, the company also commercially sells a mixture containing the component (C-3) and a nitrogen-containing compound and / or a boron-containing compound, and OP1312 is an example of a commercially available product, both of which are preferably used in the present invention. be able to.
The content of the component (C) is 1 to 70 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (B) from the viewpoint of the balance between flame retardancy and toughness. If the content of the component (C) is less than 1 part by weight, the flame retardancy becomes insufficient. The content of the component (C) is preferably 10 parts by weight or more, more preferably 20 parts by weight or more. On the other hand, when the content of the component (C) exceeds 70 parts by weight, the toughness decreases. The content of the component (C) is preferably 65 parts by weight or less, more preferably 60 parts by weight or less.
Further, in the combination of the components (C), the content of each (C) phosphorus-based flame retardant is preferably 1% by weight or more in 100% by weight of the total of the components (C).
For example, when two types of (C-1) are contained, the content ratio (weight ratio) of each (C-1) is 100% by weight of the total of (C-1) and (C-1). It is preferably 1% by weight or more. The content of each (C-1) is more preferably 15% by weight or more, still more preferably 30% by weight or more, from the viewpoint of being more excellent in flame retardancy. The content ratio (weight ratio) of each (C-1) is preferably 99% by weight or less with respect to 100% by weight of the total of (C-1) and (C-1). From the viewpoint of being more excellent in flame retardancy, it is more preferably 85% by weight or less, and further preferably 70% by weight or less.
In addition, the content ratio (weight ratio) of (C-1) when (C-1) and (C-2) are contained is 100% by weight in total of (C-1) and (C-2). On the other hand, it is preferably 1% by weight or more. From the viewpoint of being more excellent in flame retardancy, it is more preferably 15% by weight or more, and further preferably 30% by weight or more. The content ratio (weight ratio) of (C-1) is preferably 99% by weight or less with respect to 100% by weight of the total of (C-1) and (C-2). From the viewpoint of being more excellent in flame retardancy, it is more preferably 85% by weight or less, and further preferably 70% by weight or less. In addition, the content ratio (weight ratio) of (C-2) when (C-1) and (C-2) are contained is 100% by weight in total of (C-1) and (C-2). On the other hand, it is preferably 1% by weight or more. From the viewpoint of being more excellent in flame retardancy, it is more preferably 15% by weight or more, and further preferably 30% by weight or more. Further, the content ratio (weight ratio) of (C-2) is preferably 99% by weight or less with respect to 100% by weight of the total of (C-1) and (C-2). From the viewpoint of being more excellent in flame retardancy, it is more preferably 85% by weight or less, and further preferably 70% by weight or less.
In addition, the content ratio (weight ratio) of (C-1) when (C-1) and (C-3) are contained is 100% by weight of the total of (C-1) and (C-3). , 1% by weight or more is preferable. From the viewpoint of being superior in mechanical properties and fluidity, 10% by weight or more is more preferable, and 20% by weight or more is more preferable. The content ratio (weight ratio) of (C-1) is preferably 99% by weight or less with respect to 100% by weight of the total of (C-1) and (C-3). From the viewpoint of being more excellent in flame retardancy, 50% by weight or less is more preferable, and 40% by weight or less is more preferable. In addition, the content ratio (weight ratio) of (C-3) when (C-1) and (C-3) are contained is 100% by weight of the total of (C-1) and (C-3). , 1% by weight or more is preferable. From the viewpoint of being more excellent in flame retardancy, 50% by weight or more is more preferable, and 60% by weight or more is more preferable. Further, the content ratio (weight ratio) of (C-3) is preferably 99% by weight or less with respect to 100% by weight of the total of (C-1) and (C-3). From the viewpoint of being superior in mechanical properties and fluidity, 90% by weight or less is more preferable, and 80% by weight or less is more preferable.
In the present invention, the flame retardancy is improved by containing (D) a nitrogen-based flame retardant. Examples of the (D) nitrogen-based flame retardant used in the present invention include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amide compounds, aromatic amide compounds, urea and thiourea. And so on. Two or more of these may be contained. Among these, nitrogen-containing heterocyclic compounds are preferably used.
Examples of the aliphatic amine compound include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane and 1,2-diaminocyclooctane.
Examples of the aromatic amine compound include aniline and phenylenediamine.
Examples of the nitrogen-containing heterocyclic compound include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine and a triazine compound.
Examples of the cyanide compound include dicyandiamide and the like.
Examples of the aliphatic amide compound and the aromatic amide compound include N, N-dimethylacetamide and N, N-diphenylacetamide.
The triazine compound exemplified in the above-mentioned nitrogen-containing heterocyclic compound is a compound having a triazine skeleton. For example, triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, amerin, ameride, thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoiso Examples thereof include propoxytriazine and melamine polyphosphate, and melamine cyanurate, melamine isocyanurate and melamine polyphosphate are particularly preferably used.
As the melamine cyanurate or the melamine isocyanurate, an adduct of cyanuric acid or isocyanuric acid and a triazine compound is preferable, and the composition is usually 1: 1 (molar ratio), and in some cases 1: 2 (molar ratio). Additives to have can be mentioned. These are produced by known methods. For example, a mixture of melamine and cyanuric acid or isocyanuric acid is used as an aqueous slurry, and the slurry is mixed well to form fine particles of salts of both, and then the slurry is filtered and dried. By doing so, it is generally obtained in the form of powder. In addition, the above salt does not have to be completely pure, and some unreacted melamine, cyanuric acid, or isocyanuric acid may remain. When the dispersibility is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent such as a metal oxide such as polyvinyl alcohol and silica may be used in combination. Further, both the average particle size before and after being contained in the resin of melamine cyanurate or melamine isocyanurate is preferably 0.1 to 100 μm from the viewpoint of flame retardancy, mechanical strength and surface property of the molded product. Here, the average particle size is a cumulative distribution 50% particle size measured by the laser micron sizer method. As commercially available products of melamine cyanurate or melamine isocyanurate, MC-4000, MC-4500, MC-6000 and the like manufactured by Nissan Chemical Industries, Ltd. are preferably used.
The content of the component (D) is 1 to 90 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (B) from the viewpoint of the balance between flame retardancy and toughness. If the content of the component (D) is less than 1 part by weight, the flame retardancy becomes insufficient. The content of the component (D) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more. On the other hand, when the content of the component (D) exceeds 90 parts by weight, the toughness decreases. The content of the component (D) is preferably 85 parts by weight or less, more preferably 80 parts by weight or less.
The flame-retardant thermoplastic polyester resin composition of the present invention further comprises (E) aroma when the (C) phosphorus-based flame retardant contains (C-1) condensed phosphoric acid ester and (C-2) phosphazene compound. The inclusion of the group polycarbonate resin has an effect of suppressing the occurrence of bleed-out in which the phosphorus-based flame retardant of the component (C-1) or the component (C-2) is deposited on the surface of the molded product. It also has the effect of reducing the molding shrinkage during injection molding and improving dimensional accuracy.
Examples of the (E) aromatic polycarbonate resin in the present invention include aromatic homo or copolycarbonate obtained by reacting an aromatic dihydric phenolic compound with phosgene or a carbonic acid diester.
Examples of the aromatic dihydric phenolic compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4-hydroxyphenyl) propane. Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, And 1-Phenyl-1,1-bis (4-hydroxyphenyl) ethane and the like can be used. Two or more of these can also be used.
The (E) aromatic polycarbonate resin used in the present invention preferably has a weight average molecular weight in the range of 10000 to 1100,000. When the weight average molecular weight is 10,000 or more, the mechanical properties are further improved. It is more preferable that the weight average molecular weight is 60,000 or more. On the other hand, when the weight average molecular weight is 1100,000 or less, the fluidity during molding is improved. The weight average molecular weight referred to here is obtained by measuring in polystyrene conversion by gel permeation chromatography using tetrahydrofuran as a solvent.
In addition, the (E) aromatic polycarbonate resin used in the present invention has a melt flow rate (MFR) in the range of 1 to 100 g / 10 minutes measured under a temperature of 300 ° C and a load condition of 11.8 N. Is preferable, and from the viewpoint of mechanical properties, the range of 1 to 50 g / 10 minutes is more preferable.
In addition, the content of component (E) is 1 to 1 to 100 parts by weight in total of component (A) and component (B) from the viewpoint of bleed-out suppression, toughness, flame retardancy and tracking resistance. It is preferably 50 parts by weight. In particular, in terms of flame retardancy, toughness and suppression of bleed-out, the content of the component (E) is preferably 1 part by weight or more, more preferably 2 parts by weight or more, and 3 parts by weight or more. It is more preferable to have. On the other hand, particularly in terms of tracking resistance, the content of the component (E) is preferably 50 parts by weight or less, more preferably 45 parts by weight or less, and particularly preferably 40 parts by weight or less.
In the present invention, the (C) phosphorus-based flame retardant is compared with the total of (B) methacrylic resin and (E) aromatic polycarbonate resin in that the balance between flame retardancy, mechanical properties and bleed-out suppression is particularly excellent. The ratio of the total contents of (C-1) condensed phosphate and (C-2) phosphazene compound ({(C-1) + (C-2)} / {(B) + (E)})} is , 50/50 to 30/70 (weight ratio) is preferable. When the ratio of the total contents of the components (C-1) and (C-2) to the total contents of the components (B) and (E) is 50/50 or less, the components (C-1) and (C-1) and The bleed-out of the / or (C-2) component can be suppressed more effectively. On the other hand, when the ratio of the total contents of the components (C-1) and (C-2) to the total of the components (B) and (E) is 30/70 or more, the flame retardancy is further improved. be able to.
By further containing (F) an alkaline earth metal salt in the flame-retardant thermoplastic polyester resin composition of the present invention, tracking resistance, which is one of the electrical characteristics, can be further improved. Further, by containing (F) an alkaline earth metal salt, the hydrolysis characteristics and the thermal decomposition characteristics can be remarkably improved.
The salts constituting the (F) alkaline earth metal salt in the present invention include inorganic salts such as carbonates, sulfates, and phosphates, acetates, lactates, oleic acid, palmitic acid, stearic acid, and montanic acid. Organic acid salts such as. Specific examples of the (F) alkaline earth metal salt include magnesium carbonate, calcium carbonate, barium carbonate, magnesium sulfate, calcium sulfate, barium sulfate, magnesium phosphate, calcium phosphate, barium phosphate, magnesium acetate, calcium acetate, and the like. Barium acetate, magnesium lactate, calcium lactate, barium lactate, as well as magnesium salts of organic acids such as oleic acid, palmitic acid, stearic acid and montanic acid, calcium salts and barium salts, etc., these are one or two It can be used as described above. Among these, carbonates of alkaline earth metals are preferably used, and more preferably calcium carbonate is used from the viewpoint of mechanical properties and cost.
As the above-mentioned calcium carbonate, coloride calcium carbonate, light calcium carbonate, heavy calcium carbonate, wet pulverized fine powder heavy calcium carbonate, wet heavy calcium carbonate (white) and the like are known depending on the production method, all of which are the present invention. Can be used in.
These (F) alkaline earth metal salts may be treated with a silane coupling agent or one or more surface treatment agents such as organic and inorganic substances. Further, the shape of the (F) alkaline earth metal salt is preferably in the form of a powder of 10 μm or less from the viewpoint of dispersibility and the like.
The content of the component (F) is preferably 0.01 to 5 parts by weight with respect to a total of 100 parts by weight of the components (A) and (B) from the viewpoint of the balance between tracking resistance and toughness. .. When the content of the component (F) is 0.01 parts by weight or more, the tracking resistance is further improved. The content of the component (F) is more preferably 0.1 part by weight or more, and more preferably 0.5 part by weight or more. On the other hand, when the content of the component (F) is 5 parts by weight or less, the toughness is further improved. The content of the component (F) is more preferably 4 parts by weight or less, and more preferably 3 parts by weight or less.
The flame-retardant thermoplastic polyester resin composition of the present invention may further contain (G) glass fiber, which can mainly improve mechanical strength and heat resistance.
Examples of the (G) glass fiber used in the present invention include chopped strand type and roving type glass fiber. Glass fibers treated with a silane coupling agent such as an aminosilane compound or an epoxysilane compound and / or a sizing agent containing one or more epoxy compounds such as urethane, vinyl acetate, bisphenol A diglycidyl ether, and novolac epoxy compound. It is preferably used. The silane coupling agent and / or the sizing agent may be mixed with the emulsion solution and used. The fiber diameter of the glass fiber is preferably 1 to 30 μm, more preferably 5 to 15 μm.
Further, glass fibers having an arbitrary shape cross section such as circular glass fibers, elliptical glass fibers having an arbitrary aspect ratio, flat glass fibers and eyebrows-shaped glass fibers can also be used. By using flat glass fiber or eyebrows-shaped glass fiber, there are features that improve fluidity during injection molding and obtain a molded product with less warpage.
The content of component (G) is the balance between component (A) and component (B) in terms of the balance between mechanical strength, heat resistance, fluidity during injection molding, and durability of injection molding machines and molds. It is preferably 1 to 150 parts by weight with respect to 100 parts by weight in total. When the content of the component (G) is 1 part by weight or more, the mechanical strength and heat resistance are further improved. The content of the component (G) is preferably 2 parts by weight or more, and more preferably 3 parts by weight or more. On the other hand, when the content of the component (G) at the time of injection molding is 150 parts by weight or less, the fluidity at the time of injection molding is improved and the wear of the mold can be suppressed. The content of the component (G) is preferably 140 parts by weight or less, more preferably 130 parts by weight or less.
Further, to the flame-retardant thermoplastic polyester resin composition of the present invention, known additives such as an ultraviolet absorber, a light stabilizer, a plasticizer and an antistatic agent can be added as long as the object of the present invention is not impaired. One or more kinds may be contained.
The flame-retardant thermoplastic polyester resin composition of the present invention may contain a transesterification inhibitor for the purpose of inactivating the transesterification reaction catalyst or the transesterification reaction catalyst. As the transesterification inhibitor, a phosphate compound is preferably used. Phosphate compounds are a general term for partial ester compounds of alcohols and phosphoric acid. Low molecular weight compounds are colorless liquids, high molecular weight compounds are white waxy and flake-like solids, and specific examples include monomethyl acid phosphate. Monoethyl acid phosphate, monoisopropyl acid phosphate, monobutyl acid phosphate, monolauryl acid phosphate, monostearyl acid phosphate, monododecyl acid phosphate, monobehenyl acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate. , Lauryl Acid Phosphate, Distearyl Acid Phosphate, Zidodecyl Acid Phosphate, Dibehenyl Acid Phosphate, Trimethy<u style="single">Ruho</u>Sfate, and Triethyl<u style="single">Ruho</u>Examples include Sfate. Two or more of these may be contained.
Preferred phosphate compounds include long-chain alkyl acid phosphate compounds such as mixtures of mono and distearyl acid phosphate, and commercially available products are from ADEKA Corporation to "ADEKA STAB" (registered trademark) AX-71. It is a flake-like solid that is commercially available under the name and has a melting point.
The content of the transesterification inhibitor is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B) from the viewpoint of flame retardancy and thermal deformation temperature. When the content of the transesterification inhibitor is 0.01 parts by weight or more, the heat resistance can be improved. The content of the transesterification inhibitor is more preferably 0.02 parts by weight or more, still more preferably 0.03 parts by weight or more. On the other hand, when the content of the transesterification inhibitor is 5 parts by weight or less, the flame retardancy can be further improved. The content of the transesterification inhibitor is more preferably 4 parts by weight or less, still more preferably 3 parts by weight or less.
The flame-retardant thermoplastic polyester resin composition of the present invention may contain a polyfunctional epoxy compound for the purpose of improving hydrolyzability. Here, the polyfunctional epoxy compound contains two or more epoxy groups in the molecule, and a liquid or solid compound can be used. Examples of the polyfunctional epoxy compounds such as ethylene, propylene and 1-butene such as α--olefin copolymerizing the fin and glycidyl acrylate, glycidyl methacrylate, alpha, such as ethacrylic acid glycidyl, a β- unsaturated acid glycidyl ester Epoxy group-containing polymer compound, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxy Bisphenols such as benzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane- Examples thereof include glycidyl ether-based epoxy compounds, glycidyl ester-based epoxy compounds such as phthalic acid glycidyl ester, glycidyl amine-based epoxy compounds such as N-glycidyl aniline, and novolak-type epoxy resins obtained by reacting novolak-type phenol resin with epichlorohydrin. ..
As the polyfunctional epoxy compound, a copolymer of α-olefin and α, β-unsaturated carboxylic acid glycidyl ester, and a novolak type epoxy resin obtained by reacting a novolak type phenol resin with epichlorohydrin are preferable, and among them, hydrolyzable. Since the weld physical properties can be further improved, a novolak type epoxy resin obtained by reacting a novolak type phenol resin with epichlorohydrin is particularly preferably used.
The content of the polyfunctional epoxy compound is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). When the content of the polyfunctional epoxy compound is 0.01 parts by weight or more, the heat resistance can be improved. The content of the polyfunctional epoxy compound is more preferably 0.02 parts by weight or more, still more preferably 0.03 parts by weight or more. On the other hand, when the content of the polyfunctional epoxy compound is 3 parts by weight or less, the flame retardancy can be further improved. The content of the polyfunctional epoxy compound is more preferably 2.5 parts by weight or less, still more preferably 2 parts by weight or less.
The flame-retardant thermoplastic polyester resin composition of the present invention preferably contains one or more alkylene oxide units having three or more functional groups for the purpose of improving fluidity during molding processing such as injection molding. It can contain a thermoplastic compound containing. Here, the polyhydric alcohol compound refers to a compound having two or more hydroxyl groups. The polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups may be a low molecular weight compound or a polymer, and may be a trifunctional compound, a tetrafunctional compound and Any polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups, such as a pentafunctional compound, is preferably used. The functional groups of three or more functional groups include hydroxyl groups, aldehyde groups, carboxylic acid groups, sulfo groups, amino groups, glycidyl groups, isocyanate groups, carbodiimide groups, oxazoline groups, oxazine groups, ester groups and amide groups. It is preferably at least one selected from a silanol group and a silyl ether group, and more preferably has three or more functional groups that are the same or different from these, particularly fluidity, mechanical properties, and the like. In terms of durability, heat resistance and productivity, it is more preferable that the functional groups are the same.
Further, a preferred example of the alkylene oxide unit of the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups is an aliphatic alkylene oxide unit having 1 to 4 carbon atoms. Specific examples include methylene oxide units, ethylene oxide units, trimethylene oxide units, propylene oxide units, tetramethylene oxide units, 1,2-butylene oxide units, and 2,3-butylene oxide units or isobutylene oxide units. Can be done.
In the present invention, it is particularly preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as the alkylene oxide unit in terms of excellent fluidity, recyclability, durability, heat resistance and mechanical properties. In addition, it is a particularly preferable embodiment to use a compound containing a propylene oxide unit in that it is excellent in hydrolysis resistance and toughness (tensile elongation at break). Regarding the number of alkylene oxide units, the number of alkylene oxide units per functional group is preferably 0.1 or more, more preferably 0.5 or more, and further preferably 1 or more in terms of being more excellent in fluidity. On the other hand, in terms of being more excellent in mechanical properties, the alkylene oxide unit per functional group is preferably 20 or less, more preferably 10 or less, and further preferably 5 or less.
In addition, a polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups reacts with (A) a thermoplastic polyester resin and is introduced into the main chain and side chain of (A) component. In addition, the structure at the time of compounding may be maintained without reacting with the component (A).
In the present invention, the content of the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups is 0.01 to 3 with respect to 100 parts by weight of the total of the component (A) and the component (B). It is preferably a part by weight. When the content of the polyhydric alcohol compound is 0.01 parts by weight or more, the fluidity can be improved. The content is more preferably 0.05 parts by weight or more, still more preferably 0.1 parts by weight or more. On the other hand, when the content of the polyhydric alcohol compound is 3 parts by weight or less, the mechanical properties can be further improved. The content is more preferably 2.0 parts by weight or less, and further preferably 1.5 parts by weight or less.
The flame-retardant thermoplastic polyester resin composition of the present invention may contain a vinyl-based resin other than (B) methacrylic resin for the purpose of improving toughness such as impact strength. The vinyl-based resin is a resin obtained by polymerizing one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, and maleimide-based monomers. Alternatively, a rubber-based component such as polybutadiene-based rubber obtained by graft-polymerizing or copolymerizing these monomers can be mentioned. It is a preferable embodiment that the total amount of the aromatic vinyl compound, the vinyl cyanide compound, the (meth) acrylic acid alkyl ester and the maleimide-based monomer in all the monomers is 50% by weight or more.
Examples of the above aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and divinylbenzene, examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and examples of the maleimide-based monomer include acrylonitrile and methacrylonitrile. , Maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and N-substituted maleimides such as derivatives thereof. Further, a vinyl resin obtained by copolymerizing the above-mentioned monomer with a diene compound, a maleic acid dialkyl ester, an allyl alkyl ether, an unsaturated amino compound, a vinyl alkyl ether and the like can also be used in the present invention.
In addition, preferred examples of vinyl resins include methyl methacrylate / acrylonitrile, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, styrene / N-phenylmaleimide resin, and styrene / acrylonitrile / N-phenylmaleimide. Modified with a vinyl-based (co) polymer such as resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high-impact-polystyrene resin and other rubbery polymers Examples thereof include block copolymers such as styrene resins, styrene / butadiene / styrene resins, styrene / isoprene / styrene resins, and styrene / ethylene / butadiene / styrene resins. In particular, a polystyrene resin and an acrylonitrile / styrene resin are preferable, and an acrylonitrile / styrene copolymer, which is a copolymer obtained by copolymerizing acrylonitrile and styrene, is more preferably used.
Further, as the acrylonitrile / styrene resin, an acrylonitrile / styrene resin containing 15% by weight or more and less than 35% by weight of acrylonitrile is particularly preferably used.
The aromatic vinyl compound is a vinyl resin obtained by graft-polymerizing or copolymerizing an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride or an epoxy group-containing vinyl monomer with a vinyl resin. There may be. Of these, a vinyl resin obtained by graft-polymerizing or copolymerizing an unsaturated acid anhydride or an epoxy group-containing vinyl monomer is preferable.
The unsaturated acid anhydrides are compounds that share both a vinyl group that can be radically polymerized in one molecule and an acid anhydride, and specific examples thereof include maleic anhydride.
The epoxy group-containing vinyl-based monomer is a compound that shares both a vinyl group and an epoxy group that can be radically polymerizable in one molecule. Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, and glycidyl etacrilate. , Glycidyl esters of unsaturated organic acids such as glycidyl itaconate, glycidyl ethers such as allyl glycidyl ether and the above derivatives such as 2-methylglycidyl methacrylate, among which glycidyl acrylate and methacrylic acid Glycydyl can be preferably used. In addition, these can be used alone or in combination of two or more.
The amount used when graft-polymerizing or copolymerizing unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl-based monomers is 0.05% by weight or more with respect to the vinyl-based resin. Is preferable. When a large amount of copolymerization is carried out, the fluidity tends to decrease and gelation tends to occur, preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less.
Further, the aromatic vinyl compound may be a vinyl resin obtained by epoxy-modifying the vinyl resin with an epoxy agent such as peroxide, performic acid, peracetic acid, and perbenzoic acid. In this case, in order to effectively carry out the epoxy modification, it is preferable that the diene-based monomer is randomly copolymerized or block-copolymerized in the vinyl-based resin. Butadiene, isoprene and the like are preferably used as examples of the diene-based monomer. Examples of suitable production methods for these epoxy-modified vinyl resins are shown in Japanese Patent Application Laid-Open No. 6-256417, Japanese Patent Application Laid-Open No. 6-220124, and the like.
Further, a vinyl resin in which the innermost layer (core layer) having a rubber layer and the vinyl resin covering the rubber layer is formed as one kind of the outer layer (shell layer) is also preferably used, and is a core shell type having a so-called core shell type structure. Rubber is also preferably used.
The type of the rubber layer may be any one composed of a polymer component having rubber elasticity. Examples of the type of rubber layer include rubber composed of a polymer of an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene propylene component, and the like. Preferred rubbers include, for example, acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, and acrylonitrile units. It is a rubber composed of a polymer of a nitrile component such as a methacrylonitrile unit and a conjugated diene component such as a butanediene unit or an isoprene unit. Further, a rubber composed of a copolymer of two or more of these components is also preferably used.
The vinyl-based resin used for the outer layer (shell layer) is a vinyl-based resin obtained by graft-polymerizing or copolymerizing an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride, or an epoxy group-containing vinyl monomer. It may be a resin or a vinyl-based resin obtained by modifying the vinyl-based resin with an epoxidizing agent such as peroxides, perigiic acid, peracetic acid, and perbenzoic acid.
Further, as a preferable example of the core-shell type rubber, the core layer is a dimethylsiloxane / butyl acrylate polymer, the outermost layer is a methyl methacrylate polymer or an acrylonitrile / styrene copolymer, and the core layer is a butandien / styrene polymer. The outermost layer is a methyl methacrylate polymer or an acrylonitrile / styrene copolymer, and the core layer is a butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer or an acrylonitrile / styrene copolymer. Can be mentioned. Further, it is a more preferable embodiment that any one or both layers of the rubber layer and the outermost layer are polymers containing glycidyl methacrylate units.
Further, in the core-shell type rubber, the weight ratio of the core to the shell is preferably 10% by weight or more and 90% by weight or less, more preferably 30% by weight or more and 80% by weight of the core layer with respect to the entire core-shell type rubber. It is less than% by weight.
Further, as the core-shell type rubber, a commercially available product satisfying the above-mentioned conditions may be used, or it may be produced and used by a known method. Commercially available products of the multilayer structure include, for example, "Metabrene" (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd., "Kaneace" (registered trademark) manufactured by Kaneka Co., Ltd., and "Paraloid" (registered trademark) manufactured by Dow Chemical Co., Ltd. Trademarks) and "Parapet" (registered trademark) SA manufactured by Kuraray Co., Ltd., which may be used alone or in combination of two or more.
Further, in the present invention, a vinyl resin containing a vinyl resin as a branched chain of the graft copolymer may be used, and examples of the resin serving as the main chain include a polyolefin resin, an acrylic resin, and a polycarbonate resin. be able to. Either the branched chain or the main chain may be modified with glycidyl methacrylate or acid anhydride, and specific examples thereof include poly (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate (E / GMA-g). -PMMA), Poly (ethylene / glycidyl methacrylate) -g-polystyrene (E / GMA-g-PS), poly (ethylene / glycidyl methacrylate) -g-acrylonitrile / styrene (E / GMA-g-AS), poly ( Examples include polyethylene-g-acrylonitrile / styrene (Eg-AS) and polycarbonate-g-acrylonitrile / styrene (PC-g-AS) (in the above, "-g-" stands for graft and "-/". -Represents copolymerization.).
In addition, examples of the above-mentioned commercially available products include "Modiper" (registered trademark) manufactured by NOF CORPORATION, and these may be used alone or in combination with other vinyl resins.
Further, the content of the vinyl resin is preferably 0.1 to 40 parts by weight with respect to 100 parts by weight in total of the component (A) and the component (B) from the viewpoint of toughness and mechanical properties. If the content of the vinyl resin is 0.1 parts by weight or more, the toughness is further improved. The content of the vinyl resin is more preferably 0.5 parts by weight or more, and more preferably 1 part by weight or more. On the other hand, when the content of the vinyl resin is 40 parts by weight or less, the mechanical properties are further improved. The content of the vinyl resin is more preferably 35 parts by weight or less, and more preferably 30 parts by weight or less.
The flame-retardant thermoplastic polyester resin composition of the present invention may contain a resin for improving impact strength in addition to the vinyl-based resin described above. In addition to vinyl-based resins, resins that improve impact strength include ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, ethylene-butene-1 copolymers, natural rubbers, thiocol rubbers, and polysulfide rubbers. Examples thereof include acid anhydrides in which polyether rubber, epichlorohydrin rubber and ethylene are epoxy-modified with maleic anhydride, modified olefin resins obtained by epoxy-modifying with glycidyl methacrylate and an epoxidizing agent, and those having various degree of cross-linking. , Such as those having various microstructures such as cis structure and trans structure.
Examples of the modified olefin resin in which ethylene is epoxy-modified with an acid anhydride such as maleic anhydride, glycidyl methacrylate and an epoxidizing agent include ethylene / glycidyl methacrylate, ethylene / butene-1 / maleic anhydride, and ethylene / propylene /. Specific examples include maleic anhydride, ethylene / maleic anhydride, and an epoxidized olefin resin obtained by epoxidizing ethylene with a peroxide or the like. Examples of commercially available products are "Bond First" manufactured by Sumitomo Chemical Co., Ltd. "(Registered trademark) E (ethylene / glycidyl methacrylate)," Toughmer "(registered trademark) MH-5010 and MH-5020 (ethylene / butene-1 / maleic anhydride) manufactured by Mitsui Chemicals, Inc. can be mentioned. In particular, ethylene / butene-1 / maleic anhydride is preferably used because it greatly improves the impact strength.
Further, the content of the resin used other than the vinyl resin for improving the impact strength is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the component (A) and the component (B). When the content is 0.1 part by weight or more, the impact strength is further improved. The content is more preferably 0.5 parts by weight or more, still more preferably 1 part by weight or more. On the other hand, when the content is 10 parts by weight or less, the mechanical properties are further improved. The content is more preferably 8 parts by weight or less, still more preferably 6 parts by weight or less.
In the present invention, a known phosphorus-based flame retardant other than the (C) phosphorus-based flame retardant of the present invention can be contained within a range that does not impair the effects of the present invention.
The phosphorus-based flame retardant other than the above-mentioned component (C) is a phosphorus-based flame retardant containing a phosphorus component, and examples thereof include phosphaphenanthrene compounds, ammonium polyphosphate, melamine polyphosphate and phosphate esteramide, and red phosphorus. The phosphophenanthrene compound is preferably used. Two or more of these may be contained.
The phosphaphenanthrene compound is a phosphorus-based flame retardant having at least one phosphaphenanthrene skeleton in the molecule, and commercially available products include HCA, HCA-HQ, BCA, and SANKO-220 manufactured by Sanko Co., Ltd. And M-Ester. These phosphorus-based flame retardants, especially M-Ester, can be expected to react with the terminal hydroxyl group and the terminal of the (A) thermoplastic polyester resin during melt-kneading, and are effective in suppressing bleed-out under high temperature and high humidity, and are preferably used. Be done.
The above-mentioned phosphate ester amide is an aromatic amide-based flame retardant containing a phosphorus atom and a nitrogen atom, is a powdery substance at room temperature having a high melting point, has excellent handleability when contained, and has a thermal deformation temperature. A highly flame-retardant polyester resin can be obtained. As a commercially available product, SP-703 manufactured by Shikoku Chemicals Corporation is preferably used.
Examples of the above-mentioned ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and carbamyl ammonium polyphosphate. The ammonium polyphosphate may be coated with a thermosetting resin such as a phenol resin, a urethane resin, a melamine resin, a urea resin, an epoxy resin, or a urea resin which exhibits thermosetting property.
Examples of the polyphosphate melamine include phosphoric acid melamine phosphate, pyrophosphate melamine, and polyphosphate melamine such as phosphate with melamine, melam and melem. As commercially available products, MPP-A manufactured by Sanwa Chemical Industries, Ltd., PMP-100 and PMP-200 manufactured by Nissan Chemical Industries, Ltd. are preferably used. As the red phosphorus, not only untreated red phosphorus but also red phosphorus treated with one or more compound coatings selected from the group consisting of a thermosetting resin coating, a metal hydroxide coating and a metal plating coating. It can be preferably used.
Examples of the thermosetting resin of the thermosetting resin film include phenol-formalin resin, urea-formalin resin, melamine-formalin resin, and alkyd resin. Examples of the metal hydroxide of the metal hydroxide film include aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. The metal of the metal plating film is not particularly limited as long as it is a resin capable of coating red phosphorus, and examples thereof include Fe, Ni, Co, Cu, Zn, Mn, Ti, Zr and Al, and alloys thereof. Further, these coatings may be combined in two or more types, or may be laminated in two or more types.
In addition, the content of phosphorus-based flame retardants other than (C) is 1 to 40 parts by weight, compared to 100 parts by weight of the total of components (A) and (B) in terms of flame retardancy and bleed-out. It is preferable to have. If the content is 1 part by weight or more, the flame retardancy is further improved. The content is more preferably 2 parts by weight or more, still more preferably 3 parts by weight or more. On the other hand, when the content is 40 parts by weight or less, bleed-out in which a phosphorus-based flame retardant is precipitated on the surface of the molded product can be further suppressed. The content is more preferably 35 parts by weight or less, still more preferably 30 parts by weight or less.
In the present invention, a known halogen-based flame retardant such as a brominated flame retardant can be contained within a range that does not impair the effects of the present invention.
Specific examples of the bromine-based flame retardant include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, and bis (2,4,6-tribromophenoxy) ethane. Ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabrombisphenol-S, tris (2, 3-Dibromopropyl-1) isocyanurate, tribromophenol, tribromophenylallyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabrombisphenol-A, tetrabrombisphenol-A derivative, tetrabrombisphenol -A-Epoxy oligomers or polymers, tetrabrombisphenols-A-carbonate oligomers or polymers, brominated epoxy resins such as brominated phenol novolac epoxy, tetrabrombisphenols-A-bis (2-hydroxydiethyl ether), tetrabrombisphenols- A-bis (2,3-dibromopropyl ether), tetrabrombisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, tris (tribromoneopentyl) phosphate, poly (pentabromobenzyl) Polyacrylate), octabromotrimethylphenylindane, dibromoneopentyl glycol, pentabromobenzyl polyacrylate, dibromocredyl glycidyl ether, N, N'-ethylene-bis-tetrabromophthalimide and the like. Among these, tetrabrombisphenol-A-epoxy oligomer, tetrabrombisphenol-A-carbonate oligomer, brominated epoxy resin and the like are preferably used.
In addition, the content of the halogen-based flame retardant may be 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B) from the viewpoint of further improving the flame retardancy. It is preferably, more preferably 2 to 45 parts by weight, and even more preferably 3 to 40 parts by weight.
The flame-retardant thermoplastic polyester resin composition of the present invention may contain known flame retardants such as silicone-based flame retardants and inorganic flame retardants within a range that does not impair the effects of the present invention.
Examples of the silicone-based flame retardant include silicone resin and silicone oil. The silicone resin is SiO<sub>2</sub>, RSiO<sub>3/2</sub>, And R<sub>2</sub>SiO, R<sub>3</sub>SiO<sub>1/2</sub>Examples thereof include a resin having a three-dimensional network structure formed by combining the structural units of. Here, R represents an alkyl group such as a methyl group, an ethyl group and a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent.
In the silicone oil, polydimethylsiloxane and at least one methyl group on the side chain or terminal of polydimethylsiloxane have a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, and a poly. Modified polysiloxane modified with at least one selected group of ether group, carboxyl group, mercapto group, chloroalkyl group, alkyl higher alcohol ester group, alcohol group, aralkyl group, vinyl group and trifluoromethyl group, or these A mixture can be mentioned.
The contents of the silicone-based flame retardant are the components (A) and (B) in that the silicone-based flame retardant moves to the surface of the molded product due to the heat of combustion and has the effect of preventing combustion from the surface of the molded product. It is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and further preferably 0.15 parts by weight or more with respect to 100 parts by weight of the total. The content of the silicone flame retardant is preferably 4 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 2 parts by weight or less in terms of being superior in mechanical properties.
Examples of the inorganic flame retardant include magnesium hydroxide hydrate, aluminum hydroxide hydrate, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxytinate, zinc tinate, metatin acid, and tin oxide. Tin oxide salt, zinc sulfate, zinc oxide, zinc borate, zinc borate hydrate, zinc hydroxide<u style="single">、</u>Ferrous oxide, second oxide<u style="single">Iron, acid</u>Stannous, stannic oxide, ammonium borate, ammonium octamolybdate, metal salt of tungstic acid, composite oxide acid of tungsten and metalloid, ammonium sulfamate, zirconium compounds, graphite, and swelling graphite, etc. Can be mentioned.
Among the above-mentioned inorganic flame retardants, zinc borate hydrate and swellable graphite are preferable in terms of flame retardancy, and as an inorganic flame retardant having excellent flame retardancy and retention stability, a mixture of magnesium oxide and aluminum oxide, Zinc tinate, metastinic acid, tin oxide, zinc sulfate, zinc oxide, boric acid sub<u style="single">Lead, acid</u>Ferric chemicals, ferric oxide and sulfur sulfide are particularly preferably used.
The content of the above-mentioned inorganic flame retardant is 0.05 weight by weight with respect to a total of 100 parts by weight of the components (A) and (B) in that the endothermic effect of combustion heat and the combustion prevention effect due to expansion are exhibited. It is preferably 10 parts by weight or more, more preferably 0.1 part by weight or more, and further preferably 0.15 parts by weight or more. The content of the inorganic flame retardant is preferably 4 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 2 parts by weight or less in terms of excellent mechanical properties. ..
The flame-retardant thermoplastic polyester resin composition of the present invention may preferably contain a fluorine-based resin for the purpose of suppressing melt-dropping during combustion and further improving flame retardancy.
The fluororesin is a resin containing fluorine in a substance molecule, and specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetra). Fluoroethylene / Perfluoroalkyl Vinyl Ether) Copolymer, (Tetrafluoroethylene / Ethylene) Copolymer, (Hexafluoropropylene / propylene) Copolymer, and Polyvinylidene Fluoride, (Vinylidene Fluoride / Ethylene) Copolymer And so on.
Among these, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, polyvinylidenefluo Rides are preferred, especially polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymers.
In addition, the content of the fluororesin is relative to 100 parts by weight of the total of the component (A) and the component (B). However, it is preferably 0.05 to 3 parts by weight. When the content is 0.05 parts by weight or more, the effect of preventing melt-dropping during combustion is improved. The content is more preferably 0.1 parts by weight or more, still more preferably 0.15 parts by weight or more. On the other hand, when the content is 2 parts by weight or less, the mechanical properties are further improved. The content is preferably 1.5 parts by weight or less.
The flame-retardant thermoplastic polyester resin composition of the present invention may contain a mold release agent for the purpose of improving the mold release property during injection molding. Examples of the release agent include fatty acid amides such as ethylenebisstearyl amide, fatty acid amides composed of ethylenediamine and stearic acid and sebacic acid polycondensates, or phenylenediamine and stearic acid and sebacic acid polycondensates, and polyalkylene waxes. , Acid anhydride-modified polyalkylene wax and known mold release agents for plastics such as the above-mentioned lubricant and a mixture of a fluorine-based resin or a fluorine-based compound.
The content of the release agent is preferably 0.01 to 1 part by weight with respect to 100 parts by weight in total of the component (A) and the component (B). When the content is 0.01 parts by weight or more, a sufficient releasability effect can be obtained. The content is more preferably 0.02 parts by weight or more, still more preferably 0.03 parts by weight or more. On the other hand, when the content is 1 part by weight or less, the mechanical properties are further improved. The content is more preferably 0.8 parts by weight or less, still more preferably 0.6 parts by weight or less.
The flame-retardant thermoplastic polyester resin composition of the present invention may contain a filler other than (G) glass fiber for the purpose of improving mechanical strength and thermal deformation temperature.
Specific examples of the above-mentioned filler may be any of needle-like, granular and powder-like fillers, and for example, aramid fiber, carbon fiber, various organic fibers, glass beads, glass flakes, potassium silicate whisker, and wallastenite. , Silica, kaolin, talc, zinc oxide, magnesium oxide, aluminum oxide, mixture of magnesium oxide and aluminum oxide, fine silicic acid, aluminum silicate, silicon oxide, smectite clay minerals (montmorillonite, hectrite), vermiculite, mica, Examples include fluoroteniolite, zirconium phosphate, titanium phosphate, and dolomite.
The content of the filler is 1 to 100% by weight with respect to 100 parts by weight of the components (A) and (B) from the viewpoint of fluidity during injection molding and durability of the injection molding machine and the mold. It is preferably parts, more preferably 2 to 95 parts by weight, and even more preferably 3 to 90 parts by weight.
Further, the above-mentioned filler may be subjected to surface treatment such as a coupling agent treatment, an epoxy compound, or an ionization treatment.
The flame-retardant thermoplastic polyester resin composition of the present invention may contain one or more end-blocking agents such as an epoxy compound, an oxazoline compound, a carbodiimide-modified isocyanate compound and a carbodiimide compound for the purpose of improving hydrolyzability.
The content of the end-blocking agent is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the total of the component (A) and the component (B). When the content is 0.01 parts by weight or more, a sufficient effect of improving hydrolyzability can be obtained. On the other hand, when the content is 3 parts by weight or less, the mechanical strength is further improved. The content is more preferably 2.5 parts by weight or less, still more preferably 2 parts by weight or less.
The flame-retardant thermoplastic polyester resin composition of the present invention is further contained with a stabilizer in that the composition of the present invention can impart extremely good heat-resistant aging properties even when exposed to high temperatures for a long period of time. Can be done. As the stabilizer, a hindered phenol-based antioxidant, a phosphite-based antioxidant, and a thioether-based antioxidant can be contained, and they may be contained in combination.
The content of the stabilizer is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight, based on 100 parts by weight of the total of the components (A) and (B) from the viewpoint of improving heat resistance aging. More than parts, more preferably 0.03 parts by weight or more. The content of the stabilizer is preferably 2 parts by weight or less, more preferably 1.5 parts by weight or less, and further preferably 1 part by weight or less from the viewpoint of being more excellent in mechanical properties.
The flame-retardant thermoplastic polyester resin composition of the present invention can be toned into various colors by further containing one or more of carbon black, titanium oxide and pigments and dyes of various colors, and is weather resistant (light). It is also possible to improve the properties and conductivity.
The content of the pigment or dye is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight in total of the component (A) and the component (B). When the content is 0.01 parts by weight, toning, weather resistance (light) and conductive effects can be obtained. The content is more preferably 0.02 parts by weight or more, still more preferably 0.03 parts by weight or more. On the other hand, when the content is 3 parts by weight or less, the mechanical properties are further improved. The content is more preferably 2 parts by weight or less, still more preferably 1 part by weight or less.
Examples of the carbon black include channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. Carbon black has an average particle size of 500 nm or less and a dibutyl phthalate oil absorption of 50 to 400 cm.<sup>3</sup>Those weighing / 100 g are preferably used. The carbon black may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, a silane coupling agent, and the like.
Further, as the titanium oxide, titanium oxide having a crystal form such as rutile type or anatase type and having an average particle size of 5 μm or less is preferably used. Titanium oxide may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane cup, ring agent and the like.
Further, the above-mentioned carbon black, titanium oxide and pigments and dyes of various colors have various heats in order to improve the dispersibility with the flame-retardant thermoplastic polyester resin composition of the present invention and the handleability at the time of manufacture. It may be used as a melt-blended or simply blended mixed material with a plastic resin.
The flame-retardant thermoplastic polyester resin composition of the present invention can be obtained, for example, by melt-kneading the above (A) to (D) and, if necessary, other components.
Examples of the melt-kneading method include (A) thermoplastic polyester resin, (B) methacrylic resin, (C) phosphorus-based flame retardant, and (D) nitrogen-based flame retardant, and various types to be contained therein as necessary. A method of premixing additives and the like and supplying them to an extruder or the like for sufficient melt-kneading, or a method of supplying each component to a predetermined amount of an extruder or the like using a quantitative feeder such as a weight feeder and sufficiently melt-kneading. and so on.
Examples of the above-mentioned premixing include a dry blending method and a mixing method using a mechanical mixing device such as a tumbler, a ribbon mixer and a Henschel mixer. Further, the inorganic filler other than the fiber reinforced material and the fiber reinforced material may be added by installing a side feeder in the middle of the feeding portion and the vent portion of the multi-screw extruder such as the twin-screw extruder. In the case of liquid additives, a method of installing a liquid addition nozzle in the middle of the breech loader and the vent of a multi-screw extruder such as a twin-screw extruder and adding it using a plunger pump, or the breech loader A method of supplying from a unit or the like with a metering pump may be used.
The flame-retardant thermoplastic polyester resin composition of the present invention is preferably pelletized and then molded. Strands can be pelletized using, for example, single-screw extruders, twin-screw extruders, triple-screw extruders, conical extruders and kneader-type kneaders equipped with "unimelt" or "dalmage" type screws. There is a method of discharging in a shape and cutting with a strand cutter.
By melt-molding the flame-retardant thermoplastic polyester resin composition of the present invention, molded products of films, fibers and other various shapes can be obtained. Examples of the melt molding method include injection molding, extrusion molding, blow molding and the like, and injection molding is particularly preferably used.
In addition to the usual injection molding method, gas-assisted molding, two-color molding, sandwich molding, in-mold molding, insert molding and injection press molding are known as injection molding methods, but any molding method can be applied. it can.
The molded article of the present invention preferably has a comparative tracking index of 400 V or more in accordance with IEC60112. Examples of the method for setting the comparative tracking index within the above range include a method of molding the above-mentioned flame-retardant thermoplastic polyester resin composition of the present invention by the method described above.
The IEC60112 here is a safety standard for tracking resistance revised by the International Electrotechnical Commission (commonly known as IEC) in 2003, and is based on the measurement method of the comparative tracking index of IEC60112: 2003. It can be measured by using a 0.1% aqueous solution of ammonium chloride as an electrolyte solution. According to this standard, an electric field and a pollutant (electrolyte) such as dust and dirt are generated on the resin surface to partially discharge the resin, and the heat generated at that time promotes decomposition and carbonization of the resin, and finally surface insulation. It is a safety standard for tracking breakdown that causes ignition due to breakdown and local overheating, and resin materials used near electric fields such as mechanical mechanical parts, electrical and electronic parts, and automobile parts are required to have high tracking resistance.
In the molded product of the present invention, it is preferable that a phosphorus-based flame retardant-derived layer (flame retardant layer) is formed at 20 nm or more from the surface layer during combustion. The thickness of the flame retardant layer formed during combustion is determined using a time-of-flight secondary ion mass spectrometer TOF.SIMS5 (manufactured by ION-TOF GmbH) (hereinafter, may be abbreviated as TOF-SIMS). Can be done. Primary ions pulsed on the sample surface (Bi)<sub>3</sub><sup>+</sup>(30kV))) is irradiated, and the mass distribution (mass spectrum) of the secondary ions can be obtained by measuring the distribution of the time it takes for the secondary ions emitted from the sample surface to reach the detector. By analyzing the mass spectrum of the obtained secondary ions, organic substances and inorganic substances existing on the sample surface can be identified, and knowledge about the abundance can be obtained from the peak intensity. Furthermore, by using an ion beam dedicated to etching (Ar-GCIB (gas cluster ion) (5kV)) together, analysis in the depth direction is possible, and (A) thermoplastic polyester and (C) phosphorus-based flame retardant. The thickness of the flame retardant layer can be measured by analyzing the peaks of and its decomposition products. The thickness of the flame retardant layer is preferably 20 nm or more, more preferably 25 nm or more, and further preferably 30 nm or more from the viewpoint of further improving the flame retardancy. The flame retardant layer can be formed to a thickness of 20 nm or more by combining, for example, a (C-1) condensed phosphoric acid ester and a (C-2) phosphazene compound as a (C) phosphorus-based flame retardant. The upper limit of the thickness of the flame retardant layer is preferably 100 nm or less, more preferably 90 nm or less, and further preferably 80 nm or less from the viewpoint of bleed-out.
The molded product of the present invention is a molded product of a mechanical mechanism part, an electric part, an electronic part, and an automobile part, which utilizes mechanical properties such as tensile strength and elongation and excellent heat resistance while maintaining a high degree of flame retardancy. Can be used. Further, since the molded product of the present invention has a high degree of tracking resistance, it is particularly useful for parts and devices that come into contact with electricity.
Specific molded products of mechanical mechanical parts, electrical parts, electronic parts and automobile parts include breakers, electromagnetic switches, focus cases, flyback transformers, molded products for fixing machines of copiers and printers, general household appliances, etc. Housing for OA equipment, variable condenser case parts, various terminal boards, transformers, printed wiring boards, housings, terminal blocks, coil bobbins, connectors, relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, sockets, Plugs, condensers, various cases, resistors, electrical / electronic parts that incorporate metal terminals and wires, computer-related parts, audio parts such as acoustic parts, lighting parts, telegraph equipment-related parts, telephone equipment-related parts, air conditioner parts, Examples include home appliance parts such as VTRs and televisions, copier parts, facsimile parts, optical equipment parts, automobile ignition device parts, automobile connectors, and various electric parts for automobiles.
<p num="0188"> Next, the effect of the flame-retardant thermoplastic polyester resin composition of the present invention will be specifically described with reference to Examples. The raw materials used in Examples and Comparative Examples are shown below. Here,% and parts all represent weight% and parts by weight, and "/" in the resin name below means copolymerization.</p><p num="0189"> (A) Thermoplastic polyester resin <A-1> Polybutylene terephthalate resin, "Trecon" (registered trademark) manufactured by Toray Industries, Inc., and polybutylene terephthalate resin having an intrinsic viscosity of 0.80 measured at a temperature of 25 ° C for an o-chlorophenol solution were used.</p><p num="0190"> <A-2> Polybutylene terephthalate resin, "Trecon" (registered trademark) manufactured by Toray Industries, Inc., and polybutylene terephthalate resin having an intrinsic viscosity of 1.00 measured at a temperature of 25 ° C for an o-chlorophenol solution were used.</p><p num="0191"> <A-3> Polyethylene terephthalate resin, "Mitsui PET" (registered trademark) J005 manufactured by Mitsui Chemicals, Inc., a polyethylene terephthalate resin with an intrinsic viscosity of 0.63 measured at a temperature of 25 ° C for an o-chlorophenol solution was used. ..</p><p num="0192"> <A-4> Polypropylene terephthalate resin, Shell Chemicals Co., Ltd. "Cortera" (registered trademark) CP509200, polypropylene terephthalate resin with intrinsic viscosity of 0.92 were used.</p><p num="0193"> (B) Methacrylic resin <B-1> Methacrylic resin (Sumitomo Chemical Co., Ltd. "Sumipex" (registered trademark) MHF, weight average molecular weight 95,000, MFR (230 ° C, 37.3N) 2g / 10 minutes, glass transition temperature 115 ° C, Syngio Tacticity 47%) <B-2> Methacrylic resin (Sumitomo Chemical Co., Ltd. "Sumipex" (registered trademark) LG35, weight average molecular weight 100,000, MFR (230 ° C, 37.3N) 35g / 10 minutes glass transition temperature 90 ° C, Shinji Otakuchi Shichi 39%) (B') Methacrylic acid copolymer resin containing less than 50% by weight of methacrylic acid ester in the main structural unit <B'-1> Methyl methacrylate / styrene copolymer (Nippon Steel & Sumikin Chemical Co., Ltd. "Estyrene" (registered trademark) MS-300, methyl methacrylate / styrene = 30% by weight / 70% by weight).</p><p num="0194"> (C) Phosphorus flame retardant (C-1) Condensed phosphate ester <C-1-1> 1,3-Phenylenebis (di2,6-xylenyl phosphate) and PX-200 manufactured by Daihachi Chemical Industry Co., Ltd. were used.</p><p num="0195"> <C-1-2> 4,4-Bis (diphenylphosphoryl) -1,1-diphenyl, FP-800 manufactured by ADEKA Corporation was used.</p><p num="0196"> (C-2) Phosphazene compound <C-2-1> Cross-linked phenoxyphosphazene compound, cyclic phenoxyphosphazene represented by the general formula (1) (mixture of general formula (1) with n of 3 to 20) cross-linked with a p-phenylene group, Otsuka SPB-100 manufactured by Kagaku Co., Ltd. was used.</p><p num="0197"> (C-3) Organic phosphinic acid metal salt <C-3-1> An organic phosphinic acid metal salt, "Exolit" (registered trademark) OP-1240 manufactured by Clariant Japan Co., Ltd. was used.</p><p num="0198"> (D) Nitrogen flame retardant <D-1> Melamine cyanurate, MC-4000 manufactured by Nissan Chemical Industries, Ltd., and white powder with an average particle size of 10 μm were used.</p><p num="0199"> (E) Aromatic polycarbonate resin <E-1> Aromatic polycarbonate resin, A-2600 manufactured by Idemitsu Kosan Co., Ltd. was used.</p><p num="0200"> (F) Alkaline earth metal salt <F-1> Calcium carbonate and KSS1000 manufactured by Calfine Co., Ltd. were used. <F-2> A partial calcium salt of montanic acid wax and "Ricowax" (registered trademark) OP manufactured by Clariant Japan Co., Ltd. were used.</p><p num="0201"> (G) Glass fiber <G-1> A chopped strand-shaped glass fiber having a fiber diameter of about 10 μm, 3J948 manufactured by Nitto Boseki Co., Ltd. was used.</p><p num="0202"> (H) Other additives <H-1> A long-chain alkyl acid phosphate compound, "ADEKA STAB" (registered trademark) AX-71 manufactured by ADEKA Corporation, was used.</p><p num="0203"> <H-2> Vinyl resin, silicone / acrylic composite core-shell type rubber, and "Metabrene" (registered trademark) S-2001 manufactured by Mitsubishi Rayon Co., Ltd. were used.</p><p num="0204"> <H-3> Vinyl-based resin, methyl methacrylate / butadiene / styrene copolymer, and "Pararoid" (registered trademark) EXL-2603 manufactured by Dow Chemical Co., Ltd. were used.</p><p num="0205"> <H-4> Hindered Phenolic Antioxidant, Tetrakis [Methylene-3- (3', 5'-di-t-Butyl-4'-Hydroxyphenyl) Propionate] Methane, BASF Japan Ltd. "IRGANOX" "(Registered trademark) 1010 was used.</p><p num="0206"> <H-5> Fluorine resin, polytetrafluoroethylene, and "Teflon" (registered trademark) 6-J manufactured by Mitsui-DuPont Fluorochemical Co., Ltd., which act as a melt-drop (drip) inhibitor during combustion, were used.</p><p num="0207"> [Measurement method for each characteristic] In Examples and Comparative Examples, the characteristics were evaluated by the measurement method described below.</p><p num="0208"> 1. Tensile characteristics When polybutylene terephthalate resin is used as component (A) using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., the molding temperature is 250 ° C, the mold temperature is 80 ° C, and polyethylene is used as component (A). When terephthalate resin is used, the molding temperature is 280 ° C and the mold temperature is 80 ° C. When polypropylene terephthalate resin is used as the component (A), the molding temperature is 265 ° C and the mold temperature is 80 °. For evaluation of tensile properties of ASTM No. 1 dumbbell with a test piece thickness of 1/8 inch (about 3.2 mm) under molding cycle conditions where the injection time and holding time are 10 seconds in total and the cooling time is 10 seconds under each temperature condition of C. A test piece was obtained. Using the obtained test piece for mechanical strength evaluation, tensile breaking strength and tensile breaking elongation were measured according to ASTM D638 (2005), and the values were taken as the average value of the three measured values.</p><p num="0209"> Materials with a tensile elongation at break of less than 2.5% were judged to be inferior in toughness, and materials with large numbers of tensile strength at break and elongation at break were judged to be excellent in toughness.</p><p num="0210"> 2. Heat resistance Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., a test piece for evaluating the thermal deformation temperature of a dumbbell with a thickness of 1/8 inch (about 3.18 mm) was obtained under the same injection molding conditions as the tensile characteristics in item 1 above. Using the obtained test piece for thermal deformation temperature evaluation, the thermal deformation temperature was measured under the condition of a measured load of 1.82 MPa according to ASTM D648 (2005), and the value was taken as the average value of the three measured values.</p><p num="0211"> 3. Flame retardant Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., a combustion test piece having a thickness of 1/32 inch (about 0.79 mm) was obtained under the same injection molding conditions as the tensile characteristics in item 1 above. Using the obtained combustion test piece, the flame retardancy was evaluated according to the evaluation criteria specified in the UL94 vertical test. Flame retardancy is ranked in the order of V-0> V-1> V-2. In addition, materials that were inferior in flammability, did not reach the above V-2, and did not correspond to the above flame retardancy rank were excluded from the standard.</p><p num="0212"> 4. Bleed out Using the IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., under the same injection molding conditions as the tensile physical properties in item 1 above, a test piece for evaluating the tensile physical characteristics of the ASTM No. 1 dumbbell with a thickness of 1/8 inch (about 3.2 mm) was used. Obtained. The obtained ASTM No. 1 dumbbell was placed in a constant temperature and humidity chamber LHL-113 manufactured by ESPEC CORPORATION set at a temperature and humidity of 80 ° C × 95% RH for 400 hours to perform a moist heat treatment. The following bleed-out was determined by visually observing the appearance of the molded product after the wet heat treatment. A molded product that bleeds out is a molded product that greatly impairs its commercial value. A: No liquid or white powder bleed-out is observed in the molded product. B: Liquid or white powder bleed-out is observed in part or everywhere of the molded product.</p><p num="0213"> 5. Tracking resistance Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., an injection-molded 80 mm × 80 mm × 3 mm thick square plate was obtained under the conditions of a molding temperature of 250 ° C and a mold temperature of 80 ° C. Using the obtained square plate, the comparative tracking index was measured using a 0.1% ammonium chloride aqueous solution as the electrolyte solution according to the method for measuring the comparative tracking index of IEC60112: 2003. 6. Flame retardant layer thickness measurement Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., an injection-molded 80 mm × 80 mm × 3 mm thick square plate was obtained under the conditions of a molding temperature of 250 ° C and a mold temperature of 80 ° C. Using the obtained square plate, the square plate was installed horizontally to the ground at a height of 30 cm above the ground, and a burner and flame were used according to the UL94 vertical test, and the burner mouth was separated from the lower surface of the square plate by 20 mm. Then, the central part of the lower surface of the square plate was burned for 5 seconds. A time-of-flight secondary ion mass spectrometer TOF.SIMS5 (manufactured by ION-TOF GmbH) was used to pulse the area of 200 μm × 200 μm in the center of the combustion-treated surface of the burn-treated square plate to the sample surface. Ion (Bi)<sub>3</sub><sup>+</sup>(Acceleration voltage 30kV)) was irradiated, and the distribution of the time it took for the secondary ions emitted from the sample surface to reach the detector was measured, and the mass distribution (mass spectrum) of the outermost secondary ions was obtained. .. Furthermore, in order to investigate the change in the mass spectrum in the depth direction, an ion beam dedicated to etching (Ar-GCIB (gas cluster ion) (acceleration voltage 5 kV, cluster size (median) Ar)<sub>1500</sub>)) Was used to etch the combustion-treated square plate in the range of 600 μm × 600 μm in the center of the combustion-treated surface, and the mass spectrum of the secondary ions in the range of 200 μm × 200 μm in the center of the etched region was etched for the etching time. It was measured every second, and the mass spectrum of the secondary ion at each etching depth was obtained. From the mass spectrum of the obtained secondary ions, C, which is the polybutylene terephthalate (PBT) peak at the outermost surface and each etching depth.<sub>7</sub>H<sub>4</sub>O<sub>2</sub><sup>-</sup>Phosphate compound PO derived from peak and phosphorus flame retardants<sub>2</sub><sup>-</sup>The intensity of the peak was determined and plotted against the depth. The square plate that has not been burned is measured under the same conditions, the depth of the crater due to etching after the measurement is measured with a stylus type surface roughness meter, the etching rate is calculated, and the etching time is set to the depth. Converted to. At this time, C at each etching depth<sub>7</sub>H<sub>4</sub>O<sub>2</sub><sup>-</sup>PO at each etching depth when the intensity of<sub>2</sub><sup>-</sup>The flame retardant layer was defined as a depth range in which the strength of the flame retardant was 10 or more.</p><p num="0214"> [Examples 1 to 52], [Comparative Examples 1 to 27] Using a twin-screw extruder (manufactured by Japan Steel Works, TEX-30α) with a screw diameter of 30 mm and L / D35 in the same direction, (A) thermoplastic polyester resin, (B) methacrylic resin, (C) phosphorus-based Flame retardants, (D) nitrogen-based flame retardants, and other materials, if necessary, were mixed with the contents shown in Tables 1 to 8 and added from the main filling part of the twin-screw extruder. (G) Glass fiber was added by installing a side feeder in the middle of the breech loader and the vent. Further, the mixture was melt-mixed under extrusion conditions of a kneading temperature of 260 ° C. and a screw rotation of 150 rpm, discharged in a strand shape, passed through a cooling bath, and pelletized by a strand cutter.</p><p num="0215"> The obtained pellets were dried in a hot air dryer at a temperature of 110 ° C. for 6 hours, and then various molded products were obtained using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd. Various values were measured by the above measurement method, and the results are shown in Tables 1 to 8.</p><p num="0216"><tables num="1"><img id="000006" he="214" wi="159" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0217"><tables num="2"><img id="000007" he="213" wi="159" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0218"><tables num="3"><img id="000008" he="239" wi="158" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0219"><tables num="4"><img id="000009" he="242" wi="159" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0220"><tables num="5"><img id="000010" he="228" wi="159" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0221"><tables num="6"><img id="000011" he="244" wi="157" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0222"><tables num="7"><img id="000012" he="234" wi="159" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0223"><tables num="8"><img id="000013" he="188" wi="105" file="JP6056757B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0224"> By comparing Examples 1 to 7 and Comparative Examples 1 to 2, and Examples 19 to 25 and Comparative Examples 13 to 14, the thermoplastic polyester resin content of the present invention is 50 to 95 parts by weight, and the methacrylic resin content is 5 to 50. The flame-retardant thermoplastic polyester resin composition within the range of parts by weight had an excellent balance between flame retardancy and tracking resistance, with a flame retardancy of V-2 or higher and a comparative tracking index of 400 V or higher.</p><p num="0225"> Further, from the comparison of Examples 2 and 1 and 7, and Examples 20 and 19 and 25, the thermoplastic polyester resin content of the present invention was 70 to 90 parts by weight, and the methacrylic resin content was 10 to 30 parts by weight. The flame-retardant thermoplastic polyester resin composition within the range had a flame retardancy of V-0 and a comparative tracking index of 500 V or more, and was particularly excellent in the balance between flame retardancy and tracking resistance.</p><p num="0226"> Further, Comparative Example 12 and Comparative Example 23 in which (B) a methacrylic acid copolymer resin having a methacrylic acid ester of less than 50% as the main structural unit was used as the methacrylic resin had insufficient flame retardancy.</p><p num="0227"> From the comparison of Examples 2 and 8 to 9 and Comparative Examples 3 to 6, and Examples 20 and 26 to 27 and Comparative Examples 15 to 17, (C) flame retardant thermoplastic containing two or more phosphorus-based flame retardants. The polyester resin has a high toughness of 2.5% or more in tensile elongation at break while maintaining a flame retardancy of V-2 or more. In Comparative Example 6 containing OP-1240, an organic phosphinic acid metal salt, flame retardancy could be maintained, but the tensile elongation at break was 2.5% or less, and the toughness decreased.</p><p num="0228"> Further, from the comparison between Examples 51 to 52 and Comparative Examples 24 to 27, Examples 51 to 52 in which (C-1) condensed phosphoric acid ester and (C-2) phosphazene compound were used in combination as (C) phosphorus-based flame retardant. (C) The flame retardant layer was thicker and had excellent flame retardancy as compared with Comparative Examples 24 to 27 in which the phosphorus-based flame retardant was not used in combination.</p><p num="0229"> From the comparison between Examples 2 and 12 to 13 in which the content ratio of (C-1) / (C-3) was changed, the content ratio of (C-1) / (C-3) was 20/80 to 40. The flame-retardant thermoplastic polyester resin composition in the range of / 60 had an excellent balance between toughness and flame retardancy.</p><p num="0230"> From the comparison of Examples 20 and 30 to 35 in which the content ratio of (C-1) / (C-2) was changed, the content ratio of (C-1) / (C-2) was 15/85 to 85. Flame-retardant thermoplastic polyester resin compositions in the range of / 15 are superior in flame retardancy, and flame-retardant thermoplastic polyester resin compositions in the range of 30/70 to 70/30 are more flame-retardant. Was there.</p><p num="0231"> From the comparison between Examples 26 and 36 to 37 in which the content ratio of (C-1) / (C-1) was changed, the content ratio of (C-1) / (C-1) was 30/70 to 70. The flame-retardant thermoplastic polyester resin composition in the range of / 30 was excellent in flame retardancy.</p><p num="0232"> In addition, Example 20 containing (C-1) / (C-2) as a (C) phosphorus-based flame retardant and Example 26 containing (C-1) / (C-1), (C-1). From the comparison of Example 29 containing) / (C-3) and Example 28 containing (C-2) / (C-3), it is difficult to contain (C-1) / (C-2). The flammable thermoplastic polyester resin composition has an excellent balance of flame retardancy, tracking resistance, tensile strength and tensile elongation.</p><p num="0233"> From the comparison between Examples 2 and 10 to 11, the flame-retardant thermoplastic polyester resin composition having the content of the phosphorus-based flame retardant in the range of 20 to 60 parts by weight has flame retardancy and toughness. Was excellent in balance.</p><p num="0234"> Further, in Comparative Example 7 and Comparative Example 18 which did not contain (C) a phosphorus-based flame retardant, the flame retardancy was out of specification. On the other hand, Comparative Examples 8 to 9 and Comparative Examples 19 to 20 containing (C) a phosphorus-based flame retardant in an amount of more than 70 parts by weight obtained flame retardancy, but had a tensile elongation at break of less than 2.5% and toughness. Was inadequate.</p><p num="0235"> In addition, (D) Comparative Example 10 and Comparative Example 21 containing no nitrogen-based flame retardant were out of specification because their flame retardancy was not stable. On the other hand, in Comparative Example 11 and Comparative Example 22 in which (D) a nitrogen-based flame retardant was contained in an amount of more than 90 parts by weight, although flame retardancy was obtained, the tensile elongation at break was less than 2.5% and the toughness was insufficient. became.</p><p num="0236"> From the comparison between Example 41 and Example 20, the flame-retardant thermoplastic polyester resin composition containing (E) aromatic polycarbonate resin was improved in flame retardancy and toughness, and bleed-out could be suppressed. On the other hand, from the comparison between Example 20 and Example 42, the flame-retardant thermoplastic polyester resin composition having the content of (E) aromatic polycarbonate resin of 50 parts by weight or less was excellent in the comparative tracking index.</p><p num="0237"> Further, from the comparison of Examples 19 to 20 and Examples 41 and 43 to 44, the (C-1) condensed phosphoric acid ester and (C-1) condensed phosphoric acid ester with respect to the total content of (B) methacrylic resin and (E) aromatic polycarbonate resin were obtained. -2) The ratio of the total content of phosphazene compounds ({(C-1) + (C-2)} / {(B) + (E)}) is in the range of 50/50 to 30/70 (weight ratio). The flame-retardant thermoplastic polyester resin composition inside has a flame retardancy of V-1 or higher, does not cause bleed-out, and has an excellent balance between flame-retardant and bleed-out suppression.</p><p num="0238"> From the comparison between Examples 2 and 14 to 15 and Examples 20 and 38 to 39, the comparative tracking index was improved by containing (F) alkaline earth metal salt.</p><p num="0239"> Further, from the comparison of Examples 14 and 15 and Examples 38 and 39, the flame-retardant thermoplastic polyester resin composition containing calcium carbonate as the (F) alkaline earth metal salt has further improved tracking resistance. did.</p><p num="0240"> Further, from the comparison of Examples 14 and 16 and Examples 38 and 40, the flame-retardant thermoplastic polyester resin composition containing 5 parts by weight or less of (F) alkaline earth metal salt maintains the tracking resistance. A high degree of toughness was obtained as it was.</p><p num="0241"> From the comparison between Example 17 and Example 45 and Example 2 and Example 20, it can be seen that the flame-retardant thermoplastic polyester resin composition containing (G) glass fiber has improved tensile strength and thermal deformation temperature. ..</p><p num="0242"> Further, from the comparison between Examples 2 and 18 and Examples 20 and 46 to 50, it was confirmed that the effect of the present invention is exhibited even when (H) and other additives are contained as needed. did.</p><p num="0243"> The flame-retardant thermoplastic polyester resin compositions shown in Examples 1 to 5 and 8 have tracking resistance (comparative tracking index of 400 V or higher) while maintaining high flame retardancy (V-2 or higher). A flame-retardant thermoplastic polyester resin composition having an excellent balance of toughness (tensile elongation at break of 2.5% or more) and particularly suitable for materials used in the vicinity of an electric field was obtained.</p>
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Titles2
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- 難燃性熱可塑性ポリエステル樹脂組成物および成形品
- English
- Flame-retardant thermoplastic polyester resin composition and molded product
Classification
- CPC, 10
- C08L67/02
- C08L2201/02
- C09J133/10
- C08K5/0066
- C08K5/34924
- C08K5/521
- C08K5/5313
- C08K5/5399
- C08K7/14
- C08L33/10
- IPC, 9
- C08L67 00
- C08J5 00
- C08K3 26
- C08K3 38
- C08K3 40
- C08K5 521
- C08K5 5313
- C08L33 10
- C08L69 00
