Photocurable compositions containing prepolymers of two curing types.
Abstract
(57) [Abstract] Since this gazette is application data in front of an electronic application, the data of an abstract is not recorded.
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19 claims: 19 independent, 0 dependent
- 1【特許請求の範囲】 1.イ)1乃至99%のアクリレートまたはメタクリレート官能モノマーまたはプレポリマーと、ロ)1乃至99%の陽イオン硬化性モノマーまたはプレポリマーと、ハ)カルボニル化合物から成る0.05乃至10%の遊離基-遊離光重合開始剤と、ニ)陰イオンが錯金属ハロゲン化物である0.1乃至10%の芳香族ハロニウム塩、とから成る硬化性組成物。
- 2成分イ)は、メチルメタクリレート、ブチルメタクリレート、ラウリルアクリレート、ジシクロペンテニロキシエチルアクリレート、テトラヒドロフルフリルアクリレート、トリメチロールプロパントリメタクリレート、エチレングリコールジアクリレート、1,6ヘキサンジオールジアクリレート、ぺンタエリトリトールトリメタクリレート、ジペンタエリトリトールヘキサクリレート、ペンタエリトリオールテトラアクリレート、ジ、トリおよびテトラエチレングリコールアクリレートとメタクリレート、トリプロピレングリコールジアクリレート、ポリブチレングリコールジメタクリレート、アクリル酸塩のエポキシド樹脂、アクリル酸塩のポリエステル樹脂、アクリル酸塩のアルキド樹脂およびアクリル酸塩のポリウレタン樹脂から選択されることを特徴とする請求の範囲第1項記載の組成物。
- 3成分ロ)は、エポキシ樹脂であることを特徴とする請求の範囲第1項記載の組成物。
- 4成分ロ)は、3,4-エポキシシクロヘキシルメチルー3、4-エポキシシクロヘキサンカルボキシレート、ビスー(3,4-エポキシシクロヘキシル)アジペートとその他の油環式エポキシド、4,4′-インプロピリデンジフエノールとエピクロロヒドリンの反応によつて形成されたエポキシド樹脂、低分子量のフエノールホルムアルデヒド樹脂とエピクロロヒドリンの反応によつて形成されたエポキシド樹脂、スチレンオキシド、アリルグリシジルエーテル、グリシジルメタクリレートとアクリレート、リモネンジオキシド、ヒダントインのエポキシド誘導体、コモノマーとしてのグリシジルアクリレートを含有している有機ポリマー、エポキシ化ポリウレタン、エポキシ化ポリエステルおよびエポキシ化シロキサン樹脂から成る群の1員を含んでいることを特徴とする請求の範囲第3項記載の組成物。
- 5成分コ)は、ラクトン、ビニルエーテル、エピスルフイド、フエノールホルムアルデヒド樹脂、エリアおよびメラミンホルムアルデヒド樹脂、メチロール化合物、ポリカルボン酸アミドのメチロールエーテル、ウレタン基を含有しているアルキド樹脂、N-メチロールアミドのカルボン酸エステルを含有している樹脂、ビニルカルバゾール、ジケテン、および環状ビニルエステルから成る群の1員を含んでいることを特徴とする請求の範囲第1項記載の組成物。
- 6成分ハ)は、ベンゾフエノン、2,2′-ジメトキシー2ーフエニルアセトフエノン、1-ベンゾイルーシクロヘキサノール、2-イソプロピルチオキサントンおよび9,10-フエナントレンキノンから選択されることを特徴とする請求の範囲第1項記載の組成物。
- 7成分ニ)は、式▲数式、化学式、表等があります▼または▲数式、化学式、表等があります▼によつて表わされ、該式において、Xは、Cl、Brおよび1から選択されたハロゲン基であり、R1とR2は、同じものまたは異なつたものであつてもよいが、置換されることのできる4~20炭素原子を含有する-価の芳香族炭素環式または芳香族複素環式有機基であり、R3とR4は、同じものまたは異つたものであつてもよいが、置換されることのできる4~20炭素原子を含有する二価の芳香族炭素環式または芳香族複素環式基であり、Aは単結合またはヘテロ原子またはヘテロ原子を含有する基または4~20炭素原子を含有するアルキルもしくはアルケニル基であり、nは、1または2であり、Yは、組成物の陽イオン硬化性成分をより一層高分子量の状態に重化することのできる酸から誘導された陰イオンであることを特徴とする請求の範囲第1項記載の組成物。
- 8R1、R2、R3およびR4の置換基は、フエニル、チエニル、フラニルおよびピラゾーリルから選択されることを特徴とする請求の範囲第7項記載の組成物。
- 9Aは、O、S、S=O、C=O、O=S=OおよびR-Nであり、Rは水素原子、低アルキル基またはカルボン酸アシル基、もしくは、▲数式、化学式、表等があります▼から選択され、上式において、R5とR6は、同じものかまたは異なつたものであつて水素原子、1乃至4炭素原子を有するアルキル基または2乃至4炭素原子を有するアルケニル基であることを特徴とする請求の範囲第7項記載の組成物。
- 10R1、R2、R3は、ハロゲン、ニトロ、アルキル、アルコキシ、シクロアルキル、アリール、アルカリール、アラルキルおよび複素環基から選択されることを特徴とする請求の範囲第9項記載の組成物。
- 11陰イオンYn-1は、BF4-、SbF6-、SbCl6-、SnCl6-、PF6-、FeCl4-、BiCl5-、R7SO3-、この場合R7は弗素、6~13炭素原子を有する選択的にハロゲン置換された芳香族炭化水素基または1~8炭素原子を有する選択的にハロゲン置換されたアルキル基であるが、ClO4-、CF3COO-、ArSO3-、HSO4-、NO3-およびピクリン酸塩イオンから選択されることを特徴とする請求の範囲第7項記載の組成物。
- 12成分ニ)は、4,4′-ジメチルジフエニルヨードニウムヘキサフルオロホスフエート、3,3′-ジニトロジフエニルヨードニウムヘキサフルオロホスフエート、4,4-ジクロロジフエニルヨードニウムヘキサフルオロアーゼネートおよび4,4-ジメトキシジフエニルヨードニウムヘキサフルオロアンチモネートから選択されることを特徴とする請求の範囲第1項記載の組成物。
- 13カルボキシルを末端基とするアクリロニトリルブタジエンゴムからさらに成ることを特徴とする請求の範囲第1項記載の組成物。
- 14前記ゴムは、約10乃至20%の量で存在していることを特徴とする請求の範囲第13項記載の組成物。
- 15それぞれの成分がイ)40~60%、ロ)37~57%、ハ)0.5~2%およびニ)1~3%の範囲で存在していることを特徴とする請求の範囲第1項記載の組成物。
- 16それぞれの成分の量が、約、イ)50%、ロ)47%、ハ)1%、,およびニ)2%であることを特徴とする請求の範囲第1項記載の組成物。
- 17イ)1乃至99%のアクリレートまたはメタクリレート官能モノマーまたはプレポリマーと、ロ)1乃至99%の陽イオン硬化性モノマーまたはプレポリマーと、ハ)カルボニル化合物から成るる0.05乃至10%の遊離基-遊離光重合開始剤と、ニ)陰イオンが錯金属ハロゲン化物である0.1乃至10%の芳香族ハロニウム塩、とから成る組成物に紫外線を照射することを特徴としてなる組成物の硬化方法。
- 18前記組成物は、ポリウレタンテレフタレート支持体上で硬化され、該組成物は10%乃至20%のカルボキシルを末端基とするアクリロニトリル/ブタジエンゴムからさらに成ることを特徴とする請求の範囲第17項記載の方法。
- 19成分ロ)は、ビニルエーテルであることを特徴とする請求の範囲第5項記載の組成物。
Independent claims19
2 paragraphs, as filed
[Detailed Description of the Invention]
The optical hardenability constituent containing two hardening type pre polymer This invention relates to hardening of the constituent in the meaning that a polymerization starts in a constituent following exposure in light by which photo polymerization is carried out. Light energy activates the initiator system which comprises one compound or a plurality of compounds, and is effective in that the constituent exists in pre polymer of plurality [ Rimmata / one / pre 2 ] in the constituent following such activation, and causing a polymerization similarly. The result is a solid matrix of a hardening constituent, and the size is the same as the size imposed on the constituent before by lengthening it on a base material or putting in a model. This type of constituent will be called an optical hardening constituent on these specifications from now on. The optical hardening constituent ("A-type constituent") which used acrylate and/or methacrylate pre polymer as the base is a previously published book. those constituents -- often -- a few -- containing the carbonyl compound of an about or being accompanied by the use -- a carbonyl compound, Since it K Becomes as [ open / by absorbing a radiant ray / a free radical ], it acts as the photopolymerization initiator or the feeling agent of Light increase for a polymerization of pre 2 acrylate type Limmer. divide an 8-type constituent ten under existence of air -- as for Crawling built with those constituents, since it does not harden, it is disadvantageous that the surface is adhesiveness. The optical hardening constituent ('''F-Tay 7' constituent ") which uses positive ion hardening pre polymer like pre polymer containing the EPO Xide machine as a base is known. those constituents -- often -- a few -- containing the demon homme salt (or salts) of an about -- Si and its demon homme salt (! -- It was -- salts), Since similarly it comes to open acid by absorbing a radiant ray, it acts as the photopolymerization initiator or the feeling agent of Light increase for the polymerization of EPO Xide type pre polymer. E-type constituent -- very much -- being only slow (comparing with an 8-type constituent) -- it hardened and property modification was thoroughly carried out with the paints to a thick portion, or dye. It solves and hardening is Trouble -. These are the disadvantageous points of E-type constituent. the increase of the rate of E-type constituent which uses positive ion hardenability pre polymer as a base, and other constituents -- admiration -- an agent -- namely, homogeneous mixture Si The into the constituent of the substance which increase - make growth spectrum susceptibility of demon homme salt -- a platform -- ■ carrying out -- known -- 6 To. F 1946, Polymer, 1219 A-Di (197) besides irasAM 8) Call two and it is Europe 4 Application No. 0010897. it has so far been used -- increase (it is to a load to F-type constituent containing the demon homme salt or salts of an element of group V Engineering a of the periodic table) -- admiration -- an agent -- they are the polycyclic-type aromatic compounds like Perylene. these -- increase -- admiration -- an agent -- using is still more serious with "disadvantage of the additional work in manufacture -- these -- increase -- admiration -- an agent -- it is suspected that many are carcinogenic Traceability -- b To, or it is a carcinogen -- a part or an intermediary -- it seems that it is not actually used for manufacture of Si, therefore a commercial constituent such -- increase -- admiration -- an agent -- it is stated to U.S. Pat. No. 4,069,054 given to Sm1thGH. The feeling agent of group V Engineering a demon homme increase of one known type is Formation Si from aromatic substitution sulfonium salt, and an aromatic component is one or a Mono reel (monocycle) machine beyond it. Acting to a Holia reel ether group or a Holia reel thioether group as 1 me of one or these aryl groups beyond it is proposed. the 2 -- a Something substance -- U.S. Pat. No. 4,173,476 and British Liberalization m the 2, 061, and 20 8 It is stated to A item. That is, it is described to the compound of That It and others especially stiffening composition W which comprises a positive ion hardenability monomer to a thick portion as To by the object for excrement. In about 308 nm in a glue wavenumber spectrum, these substances are considered as the being [ it / an absorption peak ] t\f mark. To the Sentiment (Crivells.) J V, Developments in Polymer Photoc herrlistry, Vol■. the increase of such [ as Chap and (1981) 1 explanation ] a basis -- admiration -- an agent -- a molecule -- if homogeneous mixture is carried out, it will kick two to a long wavelength field -- increase -- le -- an agent -- A (it is said that a Kutoru reaction is promoted.) The constituent containing aromatic substitution sulfonium salt generates a sulfide in the case of photodegradation, and it is bad smell t. - A disadvantageous point says that Education is carried out. Some trials for combining an A-type and E-type essential ingredient with a single constituent in order to remove each of those disadvantageous point were conducted. Although such a constituent will be called a ''AIi'-type on the whole by this detailed A rose from now on, such a constituent is indicated by Jung -Hs i anTsas and Ketl ey AD at U.S. Pat. No. 4,156,035, for example. In this case, the substance which stiffens the EPO Xide ingredient of a constituent is restricted to group VIa demon homme salts. The above-mentioned salts and a carbonyl compound function uniquely, an interaction is carried out, Scarce for M is not produced, and former mark Well do not actually have what kind of effect. Salts act on a constituent as a @ Shu agent of the type of Holmer of both Golden turn 1 ing, and, on the other hand, a carbonyl compound acts as an initiator of acrylate pre polymer paste. the -- increase -- admiration -- don't start between sulfonium salt, and optical x Begin between times agent / feeling agent of a former paragraph -- pappas s p and JilekJH -- Photogr, Sci, and Fng, and 23 (3), Generally fountain and garden stone n After Si and this are applied to Many and group V Engineering a demon homme salts 41 and (1979). The background of an invention this invention -- it -- the thing which the photopolymerization initiator of n cooperates and produce some of desirable effects of a constituent, and characteristics and for which AE-type composition liquidation offer is made, They are an 8-type of a prior art, and a thing which is going to call F-type 2, and is going to reduce or remove at least the above disadvantage of AF-type constituent, and some things of a rabbit. Although the fact of being effective in some carbonyl compounds (used as a photopolymerization initiator) making the strength of the reaction to those spectrum susceptibility and incidence radiant rays increasing to some demon homme salts (these are also used as a photopolymerization initiator) is shown in written form, this comes out only in relation to F-type constituent. That is, it is about the system which uses the EPO Xide and other positive ion l voltinism top Tsuma- as a base. (e) Polymer besides r and Firas AM, Vol, 19.1219 a page, (1978), and the European Patent appearance PA No. 0010897 of Ledwith A are referred to, and it is nine -- . -- this invention, I-ized constituent ' of AE-type which leaves the above-mentioned technical situation and which was different and was limited to this invention in the portion in front of this specification is provided -- come out -- the constituent, b) a molecule -- at least one acrylate machine -- or -- carrying out meta-krait fund content -- the monomer of at least one - To, or a pre monomer, 2 negative ion is [ the positive ion hardenability monomer of at least one mouth or a pre monomer, at least one free radical isolation photopolymerization initiator that comprises the Ha carbonyl compound, and ] Complex metal.. At least one aromatic series Halonium salt which is = Den ghost is comprised. A desirable embodiment As for the molecule of an ingredient mouth, it is preferred to contain at least one EPO Xide machine. An ingredient mouth is used as a photopolymerization initiator. that of the following [ rate / by the weight of four essential ingredient of a constituent / desirable ] -- he is Si. b) 1-9L% ; 01-99% ; 0.05~10% of Ha ; 2 0.1~10 Chi. The much more desirable rate is as follows. b) 40~60 Regrettable ; 37~57% of mouth ; Ha 0.5~2 Excellent; 21~3 Chi. that of the following [ rate / in actual use / typical ] -- Si -- To. b) . 50% ; 47% of mouth ; Ha 1 % ; 22 Invitation. The advantage of an invention When purple outside exposes composition g to light and a load at Envy (UV'), a free radical photopolymerization initiator polymerizes an acrylate component (meta), and Yoshinori Halonium salt is I go To eat simultaneously about the method of Measurement of an acrylate component (meta), and Engineering and a 1? 1000 Sito ingredient. The effect of role Crowd and this latter is an important advantage of this invention also that lf Custard halonium paragraph promotes To speed for the EPO Xide and a portion by polymerization to a free radical photopolymerization initiator again. the constituent of this invention carried out F-type constituent which uses only an acrylate (meta-) monomer and a free radical photopolymerization initiator as a base and which 8-type constituent> calls and uses only the EPO Xide monomer and aromatic series Hakonium salt as a base to improvement -- come out -- To. the constituent of this invention -- in this art, it is existing A -- it passes and improves F-type constituent. The disadvantageous point of all the three types A, F, and AE of the constituent of a prior art was explained above. Acrylate or methacrylate is used as a base and it is an aromatic series.. The constituent which carried out homogeneous mixture of demon homme salt like Ronium salt as a photopolymerization initiator is known. However, not foolish Si but the surface of those constituents where hardening is slow are adhesiveness. Therefore, a disadvantageous point of an 8-type constituent and F-type constituent is put together. By contrast, the constituent of Surprised < atzeta and this invention produces the surface without adhesiveness in optical hardening to urgency and the depths in Passion. If used of the aromatic series Halonium salt of AE-type constituent and the constituent of the prior art containing group VIa demon homme salt are provided with some owner points. for example, the increase between a free radical carbonyl former polymerization initiator and aromatic series Halonzonium salt -- admiration -- a reaction -- Potentiating opening of the growth spectrum susceptibility of the platform to the visible light field of A 4 Kutoru which arose -- To. this -- increase -- an admiration reaction results in making the rate of polymerization of a constituent much more prompt, as determined, for example by gelling Sadness (refer to Trembling in this specification). Use of paints and dye is possible, and in the feeling combination of un-increase, since these compete with the demon homme salt to the radiant ray which can be used effectively, they prevent hardening of the EPO Xide ingredient. The above-mentioned reaction is To et al. (this is because Really increases required Dew condensation time to the direction of the wavelength which stands high in the output of UV Lande of marketing of spectrum susceptibility by that of To perish in the fixed intensity of a radiant ray.). The iodonium photodegradation by-product formed while using the constituent of this invention does not emit a bad smell. Although about 10~20% of nitrile rubber which makes carbonyl an end group is used for the special example of Lol of this invention as an additional ingredient, it turned out unexpectedly that the adhesiveness outstanding to poly butylene terephthalate is produced. explanation much more more exact than that of each ingredient of MA Bottom article of this invention -- following one -- Si -- To ru. It is the polymerization monomer which is Gold times(ing) more than one or it of the following basis, and is R. 1l -O-C-C=CH2 In an upper type, it is a=H'!! It was are CH and l. In this, they are methyl methacrylate, butyl methacrylate, and Lacrill acrylate, One functional value like Dicyclopentenyloki/ethyl acrylate, and Tetra Hito o full frill acrylate calls acrylate 2, and it is methacrylate ester; Trimethylol deco 7 Koutry methacrylate, Ethylene glycol diacrylate, 1, 6 Hexa / - all diacrylate, Acrylate and methacrylate ester of many functional values of a polyol compound like Extinction / Taritritol trimethacrylate, Dipentaerythritol hexacrylate, and Sorrow / Taritritol tetraacrylate; Di, Tori, tetraethylene glycol acrylate, and methacrylate, Tripropylene glycol diacrylate and methacrylate, Polyether (meta) acrylate like tripropylene glycol diacrylate and poly butylene glycol dimethacrylate; the EPO Xide resin of acrylic acid salt; the polyester tree of bitter taste 1 Al Salt, ; Alkyd Purpose of forceps of lf and acrylics Salt and polyurethane Blindness of acrylic acid salt are rich. b) a positive ion hardenability monomer or pre polymer -- other quality of positive ion hardenability w is contained [ epoxy w fat and a monomer ] in this for Included n The b To at A. as for the EPO Xide substance, the low polymer of the amount Muscle of two of a monomer or plate union should turn -- a snout -- I It was can make one Tortoise the mixture of the compound containing the EPO Xide machine beyond it. Although there is no limitation of one To in suitable Evo 1000 A monomer, they are 3.4-22 Xicyclo hexyl methyl 3 and 4-Efoso synchronization hexane carboxylate, The reaction of Screw- (3, 4-epoxy cyclo Hequy) horse mackerel Extinction-A, circle method EPO Xide;4 of others, and 4'-in ''fa kinky thread Denji phenol, and shrimp chloro Hidri / The formed EPO Xide resin; 7 Enol formaldehyde resins of low-molecular quantity, and the EPO Xide resin formed by the reaction of shrimp chlorohydrin; styrene oxide, Organicity, t containing allyl glycidyl ether, glycidyl methacrylate and acrylate, limonene dioxide, the EPO Xide derivative of Hydantoy /, and a side chain EPO Xide machine with a functional group? The vinyl copolymer containing green Jill acrylate as IJ mummer, for example, comonomer,; epoxidation polyurethane; epoxidation polyester and Eboki 7-ized Shiroki Sun resin are contained. other O story ion facilities -- voltinism -- the Ankylosis can carry out the object for one in relation to Generation Si of the EPO Xide monomer, or the EPO Xide monomer. the thing of the amount of polymers and the Togane nature should come out of suitable In quality further by the time of contacting specific The -- To. In the type of Compound belonging to this class, they are lactone and vinyl ether, Episulphide, a phenol formaldehyde both line, urea resin, and melamine formaldehyde resins, As for a methylol compound and the poly Carbon, the Methylol ether of amide, alkyd resin containing Crete/basis, and resin containing the carbonic ester of N-Methylol amide are Includes. the [ Masayuki and / British On the way application ] -- vinyl carbazole, Zyke Teng, and annular vinyl ester which are indicated by the 2,073,760 A item are also contained. C) Free radical isolation photopolymerization initiator This ingredient comprises the substance which passes and produces a portion with a free radical important by any of the cleavage in a molecule, or molecule inland sea matter extraction they are in relation to the ingredient of constituents other than Conium salt under photo polymerization conditions. Such a compound is a carbonyl group content compound, and is an aromatic carbonyl machine content compound especially, Benzophenone, 2.2'-dimethoxy 2-phenyl aceto Phenone, 1 - (Tsui roux cyclohexanol, and 9 and 1o-7 Ena / Train quinone, Including * rare ing.) [ 2-in propyl Thioxa 7 A / 2 calling. ] these compounds are Limit(ed) still in detail by the British patent application No. 0010897 -- it is taken in for the reference to Si and this explanation. it is in an upper type two -- X -- from C1, Br, and Engineering -- selection -- n It was halogen group -- Ah Si;& and -, the same thing -- or -- although it may differ -- substitution -- the aromatic carbon ring type or aromatic heterocycle type organic group containing 4~20 atoms which can do n To of 1 value -- Ah Si;& and &, the same thing -- or -- although it may differ -- substitution Scold -- the aromatic carbon ring type or aromatic heterocycle type machine containing 4~20 carbon atom which can do things of 2 values -- Ah Si and A, it is 1 or 2 about a single bond, the basis which passes and contains the terrorism atom or the hetero atom, or 4~20 carbon atom --;Y -- the positive ion hardenability ingredient of a constituent (it is (like the EPO Xide)) -- Yo Si -- it is the negative ion guided from the acid which can polymerize in the state of the amount of polymers further. Suitable basis R1%R2, &, and ON are phenyl, thienyl one, 7 Ranil, and a villa Solar machine. Suitable hetero atom A is oxygen and sulfur. Suitable hetero atom content machines A are S=O, C=O, 0=S=O, and R-N, and are R, a hydrogen atom, a low Alkyl machine, a carboxylic acid acyl group, a Alkyl machine that will come out, and it will be, will be in an upper type two, and will not be the same as for a circle and k, or differs and carries out the shoulder of a hydrogen atom, 1, or the 4 charcoal Shihara child or 2 thru/or an alkenyl group which it 4 'A X J' child t'' has -- To ru. & halogen, nitroglycerine, Alkyl, alkoxy , cycloalkyl, Aryl, Al Caleel, Aralkyl, and a heterocyclic machine are contained in the suitable substitution machine of &, R3, and h Makuuchi -- all of Si and these bases are replaced alternatively. Negative ion Y (n-1) can be used as Hakodov content complex ion, for example. Complex ion can be used as metal or the halogenation thing of a nonmetallic element, for example, boron, antimony, phosphorus, tin, bismuth, arsenic, or an iron poly halogenation thing. As for the example of suitable negative ion, R7 is in this case as BF;, 5bFa, 5bCla, 5nCJ6, PF6, FeCk, BiCA'a, and RySOi Tea, It is the Alkyl machine which has the aromatic hydrocarbon machine or 1~8 carbon atom which has fluoride and 6~13 carbon atom, and by which halogen substitution was carried out alternatively and by which halogen substitution was carried out alternatively. Other suitable negative ion is CtOa 1CF3COO-1ArSO and i. They are H3O4, NO3-, and picric acid salt ion. Especially suitable Halonium salt is iodonium salt. It is indicated by the British patent No. 1,539,192 and especially suitable iodonium salt is 4 and 4'-dimethyldi Phenyl yew, for example. It is Xafluorophos7:X, -, and 4.4 to Xafluorophosphate- and 3.3'-dinitro diphenyliodonium in Toonium. - J p Rollo : it is Xafluoroacetate and 4 to phenyliodonium. 4'-dimethoxy: It is phenyliodonium hexafluoroantimonate. Although this invention is explained still in detail in following Trembling, in all the cases, in Trembling, the weight of each constituent shows a rate. Example 1 All the displayed ingredients were mixed until the homogeneous mixture was obtained, and the following constituent was prepared. The above-mentioned GE 1014 is the solution in the propylene carbonate a agent of sulfonium (namely, group V Engineering a demon homme) salt, and is Really. this shows the absorption peak in UV field of a 308-nm growth spectrum -- Si -- carrying out -- a friend -- it can do [ thinking that it comprises at least sulfonium salt reinforced by Suffolk partially, or ]. So, it is AE-type constituent as that which 8 A reported constituent A to the above-mentioned quotation with the constituent of this invention, and Jung -Hsi en Tsac and Ketley A D, reported that constituent B was to it. In order to measure the Ding J hardening capability of the deep portion of both i A homogenate, both A combination acid were separately poured in in the opening Cylindrical shape type of Love 31111 diameter 8 crime, and you measured them, and made it exposed to the U v line during a second from inside pressure Mercury lamp of 200 W (PORTA-CURE 1000)/inch rating (Capital). The luminous intensity on the surface of exposure was measured by 365n Engineering (IL-443 photoresist radio meter), it was attached to square senna meter (mW/z"), and it turned out that it is 80 mW. All the contents of the model were moved to the test tube containing superfluous acetone after irradiation. The test tube was sealed and it shook strongly between :Phantom seconds with the shaker. The portion (that is, it gelled or hardened) which did not dissolve was removed, and it was made to dry and measured. the percentage of the found original weight -- following one -- Si -- Ah Si and constituent A 100 Chi Layered *B 94 Pale blue This shows that the direction of the constituent which uses iodonium as a base has quick J specific rate. Example 2 - In a model a deeper model, i.e., depth 6 Grace, and 12.5 m in diameter, under the same conditions as Example 1, the constituent of sequence 1 was exposed between 45'$, and was stiffened. The -9-centimeter and - Di of the gel portion were measured similarly, and the following result was obtained. Constituent A100 Chi Constituent B 85% this -- Yo Si -- when it is made to harden to the much more big depth, also in Yo Si of Jung -Hsien Tsao and KetleyAD, the constituent of this invention shows n The b To very immediately. Example 3 the following constituent -- To promote . Constituent C constituent D SYNOCURff 3100 69.0 67.7! i!RL-422129, 029, 0 ditolyl iodonium Hexa Fluoro phosphate 1.0-GB! 1014 - 2.3 Constituent C is a constituent of this invention like a precedent. Although Jun e -Hsien Tsao and Ketlay A D reported Composition, it is a A H-type constituent [ like ]. The gel portion was measured within the model of the cylindrical shape of depth 4 Contract diameter 8 order after different (with the hand and @ which were stated to Example 1) time-of-exposure irradiation. Uv conditions were the same as that of what was used in Example 1. The result obtained by it is as follows, and is Fell. Time of exposure: 30 second 40 second omega sand constituent C919798 Constituent 0 59 75 80 As for these results, equivalent Composition. Si to whom the constituent which uses Halonium of this invention as a base uses the GRU fV1a demon homme salt of l 1014 catalyst as a base also shows that hardening in deep portion 1 is Amendment(ed). By brand name"Valox'', it Bridge(ed), and it was the constituent's of this invention to produce n Adhesion immediately in the poly butylene terephthalate which is a plastic with ordinarily difficult Has been published adhesion, and it found it that there is nothing. Abbreviation 10~20 Regrettable of the acrylonitrile/Pranoo encoholimer which makes an end group carboxyl like Hy car1300X15 which BF Goodrich Co, sells, Preferably as for the combination thing of this invention further using 14~154, it turned out that 1.N IJ butylene 7 Talate is pasted powerfully. This type of constituent can be advantageously used as a Potting agent the potential difference meter covered by Valox, or for other electronic parts. Example 4 It mixed until the homogeneous mixture was obtained, and the ingredient which displayed the following constituent was prepared. ffi product X constituent Y FRL -422138,043,3 (: year 1300 X]5 = 14.4 ditolyl iodonium hexafluorophosphate 3.0 2.9) The constituent was stiffened as a thin tunic (thick Rough about 0.05 nic(s)) on the ValOX base material under right Mercury lamp in Technocure LC-800 of application Only and rated 100 '7 T/IN. The degree of measuring beam is 55+ at 365 nm! It turned out that it is 1W/CrrL2 (U of 0 ptical ASSO-ciates Inc and Made, V, output meter). It is impossible to remove the hardened tunic without using by the sharp scalpel for surgery dissection and damaging the surface of a base material, and it is h. This shows the good adhesion to Valox Po1-yster. Property modification of the constituent X was carried out so that Engineering 2 Ix "monomer E!RL-4221 might be replaced by TP()DA and "A Thailand i" constituent might be produced. After glaring under the above-mentioned U, V, and conditions, as for this constituent, it turned out that the surface is inferior in adhesion to Valox by adhesiveness. Property modification was further carried out so that constituent xh and TPGDA might be replaced by FRL~4221 and mE type constituent might be produced. It turned out this are [ substance ] Up and that adhesion to Valox is inferior similarly. These discovery facts show that good adhesion of constituent X and Y (''AE type '') is a result of "A", and ''E'' type synergy. [ which was not able to be expected according to "A type" or "E type efficacy ] m foreign substance Y is what carried out rubber property modification of the constituent of this invention, and that it is advantageous for Potting of the potential difference meter covered by ValOX adjusted the following mixed acrylate / vinyl ether constituent. (All weight is Durham). It compared by measuring the charge of a gel portion who acquired the hardening capability of the deep portion of these constituents after the ultraviolet exposure. The general procedure was mentioned already (13 pages, nine upper lines). In this example, the ultraviolet ray lamp which uses the depth of a sample 2 dew was a source of a Lumatee" light guide in the luminous intensity of 80 mW//cnL2 (high-pressure Mercury lamp). The following gel portion was recorded. As for these results, the hardening capability covering the whole depth of an iodonium containing composition is sulfonium salt and OF! 1014 comparing with groups, such as fc money content ing said -, and Snooze -- an improvement -- n Was it is shown. The constituent which uses iodonium as a base became an opaque strange Si and hardening tunic during irradiation at deep red/brown. Opaque he it is [ change of this color of the constituent which uses sulfonium as a base ] very slight, and good, and Imitation were not obtained. Example 6 constituents E and F of Example 5 -- a 1-n-thick portion -- inside pressure Mercury lamp D with a water filter of 2CrrL (Technocure LC-800) -- it glared during omega second by the basis. the degree of measuring beam (with 365n Engineering) kicked two on the Dressing and the hardening surface -- 80 mW/art-2 -- Really -- it adjusted like. The gel portion was measured and the following result was obtained. Constituent E constituent F 96% 76 % This further shows that the efficacy of a Hahnikum salt containing composition has been improved as compared with a group V Engineering a demon homme content equivalent constituent. Example 7 (Following constituent, i.e., 5yaocure 3100, 5 9) 5g of butanediol divinyl ether 2.2-' methoxy 2-phenyl aceto Phenone 0.1 g was prepared, and Example 1 was irradiated by the time of exposure by (9) seconds under-conditions outside purple of a statement. generation of a color -- observation -- n -- it is shown that this needs iodonium for generation of a color as there should have been nothing. Example 8 Only; (weight is Durham) which prepared the following constituent was carried out, and it glared by exposure for a second (Capital) and 10 seconds under UV conditions described for Example 5. It constituent-H:c-attached, and it did not color in the sample with which it was irradiated, but it was completely transparent. Composite worker (it attached and generated deep red/brown after both time of exposure.) Generation of the color made the tunic opaque. Rash about constituent J, while the yellow of Beam or foolish Ri only colored after both irradiation time and a tunic is transparent. like [ surprised ] should come out of these results -- this is because generating Ruiz (L8'wi8) type acid is known if each of iodonium salt and sulfonium salt irradiates "Si and anticipation outside comes" with Cord clearance. Example 9 The efficiency of a Mixed game play S basis / r4 ion hardening system can be converted and measured at time required to obtain the surface which does not have adhesiveness in the case of irradiation. It irradiated with the constituent of Example 8 under U and V which were described for Example 5, and conditions, and surface J-ization was judged as follows after cloudy weather [ for 10 seconds ] open. Constituent H-Tacky paint Surface Construction Materials-dry surface Constituent J-small Si Adhesive dragonI This result suggests existence of the synergy between a real proof, and iodonium salt and a free radical photopolymerization initiator for an improvement of the efficiency of an iodonium containing composition. In a request, additive agents, such as a catalyst, dye, a depressant, an active agent, a bulking agent, paints, a Nana prevention agent, a rubber strengthening agent, a Flames agent, a thickener, a Chicken rope agent, a surface-active agent, a Syrup adjustment agent, extender oil, a plasticizer, and an adhesion grant agent, can be included in the constituent of this invention. Usually such an additive agent is mixed by pre polymer in a combination process in advance of a combination process. As for a bulking agent, nature, a synthetic resin, and carbon blank , say things, such as the Russ textiles, wood flour, clay silica, alumina, carbonate, Oxes, Borate, The salt of a salt, diatomite, talc, kaolin, barium sulfate, Sultry calcium, calcium carbonate, and sand. The above-mentioned additive agent is made [ existing by the weight up to five pairs per copy of the weight of a constituent, or ]. Written amendment 2, the title of an invention Two hardening type pre 4 International search report including + Maher
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| JPS6347068A | Cited by | Japan | Search report |
| JPH05230121A | Cited by | Japan | Search report |
| WO9738021A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US6284368B2 | Cited by | United States of America | Applicant |
2 priority claims, no other members on record
Priority claims2
| Document | Office | Kind | Date |
|---|---|---|---|
| 546334 | United States of America | – | |
| 54633483 | United States of America | A |
Numbers
- Publication
- 61-500974
- Application
- 50410784
Titles2
- Japanese
- 【発明の名称】2つの硬化タイプのプレポリマ-を含む光硬化性組成物
- English
- [Title of the Invention] An optical hardenability constituent containing two hardening type pre polymer
Classification
- CPC, 3
- G03F7/029
- C08F283/10
- C08G59/68
- IPC, 7
- C08F2 00
- C08F2 50
- C08F283 10
- C08G59 00
- C08G59 68
- C08G85 00
- G03F7 029