Functionalized poly(arylene ether) composition and method

The present invention relates to a bifunctional poly (arylene ether) composition.

Curable compositions containing a reactively terminally sealed poly (allylene ether) resin and a copolymerizable monomer are described, for example, in US Pat. No. 5,01922 by Nelissen et al., No. 6352782 and No. 6352782 by Yeager et al. It is described in 6627704 and Fan's U.S. Legal Invention Registration No. H521. While the compositions described in these documents are useful in a wide variety of thermosetting applications, existing formulations lack the balanced properties desired in the manufacture of plastic encapsulation electronics. In particular, there is a need to improve fluidity during molding without impairing physical properties after curing such as rigidity and impact strength.<patcit num="1"><text>U.S. Pat. No. 5071922</text></patcit><patcit num="2"><text>U.S. Pat. No. 6,352,782</text></patcit><patcit num="3"><text>U.S. Pat. No. 6,672,704</text></patcit><patcit num="4"><text>US Legal Invention Registration No. H521</text></patcit><patcit num="5"><text>U.S. Pat. No. 4,760,118</text></patcit><patcit num="6"><text>Japanese Unexamined Patent Publication No. 60-115609</text></patcit>

<p> The curable composition with an improved balance between mold flow and physical properties after curing is a difunctional poly (arylene ether) having an intrinsic viscosity of about 0.05 to about 0.30 dl / g at 25 ° C. Includes olefinically unsaturated monomers.</p><p> Hereinafter, a method for producing a curable composition, a cured composition, and other embodiments including an article composed of the cured composition will be described in detail.</p>

As a result of diligent research, the present inventor has shown desirable properties such as high glass transition temperature, low coefficient of thermal expansion and low dielectric constant that are usually associated with poly (allylene ether) thermosetting resins, and is currently preferred in the market. We have found a composition that exhibits molding properties similar to those of the epoxy thermosetting resin. Early studies showed that the composition cured rapidly, but showed undesired fluidity in the early stages of curing. Extensive experiments have shown that lowering the intrinsic viscosity of the functionalized poly (allylene ether) improves fluidity, but this change also reduces the stiffness and impact strength of the cured composition. Further experiments revealed that by using a functionalized poly (allylene ether) having a low intrinsic viscosity but an increased polymerizable functional group, the fluidity can be improved without impairing the physical properties after curing. An unexpected finding was obtained. Especially when the poly (arylene ether) has two polymerizable groups (ie "bifunctionalized" poly (arylene ether)) and has an intrinsic viscosity of about 0.05 to about 0.30 dl / g at 25 ° C. It has been found that a substantially improved characteristic balance can be obtained.

One embodiment is a curable composition comprising a bifunctional poly (arylene ether) having an intrinsic viscosity of about 0.05 to about 0.30 dl / g (dL / g) at 25 ° C and an olefinically unsaturated monomer. .. Within the above range, the intrinsic viscosity of the bifunctional poly (arylene ether) can be more specifically about 0.08 dL / g or more, and more specifically about 0.12 dL / g or more. Similarly, within the above range, the intrinsic viscosity of the bifunctional poly (arylene ether) can be more specifically about 0.25 dL / g or less, and more specifically about 0.20 dL / g or less.

As used herein, a bifunctional poly (arylene ether) is a poly (allylene ether) having a polymerizable carbon-carbon double bond at both ends of the molecule. In one of the methods for producing such a molecule, first, poly (arylene ether) having hydroxy groups at both ends of the molecule (dihydroxypoly (arylene ether)) is produced, and then dihydroxypoly (arylene ether) is used at both ends of the molecule. React with a sequestering agent sufficient to form a polymerizable sequestering group.

There are several known methods for obtaining dihydroxypoly (arylene ether) resins. First, monovalent and divalent phenols, for example, US Pat. Nos. 4521584 and 4677185 by Heitz et al., US Pat. No. 5021543 by Mayska et al., US Patent Application Publication No. 2003/0194562 by Ishii et al., W. Risse et al., Makromolekulare Chemie (1985), Vol. 186, No. 9, pp. 1835-1853, and V. Percec et al., Polymer Copolymerization may be carried out as described in Bulletin (1990), Vol. 24, No. 5, pp. 493-500. Second, monohydroxypoly (arylene ether) resins are used as oxidants, as described, for example, in US Pat. No. 3496236 of Cooper et al., No. 5880221 of Liska et al. And No. 6569882 of Hwang et al. It may be reacted with divalent phenol in the presence of. Third, monohydroxypoly (arylene ether) resins, for example, White's US Pat. Nos. 4140675 and 4165422 and 4234706, Braat et al. 6307010, and Aycock et al.'S European patent application publication. It may be equilibrated with diphenoquinone as described in No. 550209. Fourth, dihydric phenols and dihalophenol sulfones are used, for example, Percec's US Pat. Nos. 4,562,243 and 4,663,402 and 4,665,137 and Hayase's 5,965,663, and Fan's U.S. Legal Invention Registration No. H521. As described in No., copolymerization may be carried out in the presence of a base. Fifth, a dicarbonyl adduct can be formed from a dihydroxyaromatic compound, the dicarbonyl adduct can be oxidized to the corresponding diester and the diester hydrolyzed to give a hydroxy-terminated arylene ether. This method is described, for example, in US Pat. No. 4,873,371 of Yeager et al. Sixth, the monohydroxypoly (arylene ether) resin may be reacted with formaldehyde in the presence of an acid catalyst to form a dihydroxypoly (arylene ether) having an internal methylene group. This method is described, for example, in W. Risse et al., Mcromolekulare Chemie (1985), Vol. 186, No. 9, pp. 1835-1853. Seventh, the divalent phenol may be copolymerized with 4-halo-2,6-dialkylphenol in the presence of a base. This method is, for example, W.

Dihydroxypoly (arylene ether) can be converted to bifunctional poly (arylene ether) using a known method of adding a polymerizable functional group to a poly (arylene ether) resin. Such a method is also called "blocking" of poly (allylene ether), so such reagents are also called "blocking agents". For example, the hydroxy group of poly (arylene ether) can be used, for example, in US Pat. No. 3,375228 by Holoch et al., No. 4165422 by White, No. 5071922 by Nelissen et al., No. 6352782 by Yeager et al. It may be reacted with an acid anhydride as described in No. 6384176. As another example, the hydroxy group of poly (arylene ether) is released under conditions suitable for forming ester bonds, as described, for example, in US Patent Application Publication No. 2003/0194562 of Ishii et al. It may be reacted with an acid. As another example, the hydroxy group of the poly (arylene ether) may be reacted with an acid halide, for example, as described in US Pat. No. 3,375,228 of Holoch et al. And No. 4165422 of White. As another example, the hydroxy group of poly (arylene ether) may be reacted with ketene, for example, as described in US Pat. No. 3,375,228 of Holoch et al. Yet another example is the hydroxy group of poly (arylene ether), which is a haloalkyl group under basic conditions, as described, for example, in Percec's US Pat. No. 4,562,243 and Fan's US Pat. May react with. Although not all of the above documents teach reactions with sequestering agents having ethylenically unsaturated groups, the methods described may be adapted for this purpose. For example, the acid halide blockade of Holoch et al., US Pat. No. 3,375,228 and White, No. 4165422, can be used with chlorides of acrylic acid or chlorides of methacrylate. In one embodiment, a sequestering agent and dihydroxypoly (a) A (meth) acrylate blocking group is formed by the reaction of (lealene ether). (Meta) acrylic anhydride is a suitable sequestering agent for this purpose. It will be understood that the prefix "(meth) acrylic-" includes both "acrylic-" and "methacryl-".

In one embodiment, the bifunctional poly (arylene ether) has the structure of the following equation.

<chemistry num="1"><img file="JP5147397B2_D0001.tif" /></chemistry>In the formula, each Q¹Is independently halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Hydrocarbyloxy, a halogen atom and an oxygen atom separated by two or more carbon atoms C₂~ C₁₂Halohydrocarbyloxy, etc., each Q²Independently hydrogen, halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Hydrocarbyloxy, a halogen atom and an oxygen atom separated by two or more carbon atoms C₂~ C₁₂Each x is 0 to about 100 independently, and each R is provided, provided that the total of x is 3 or more, such as halohydrocarbyloxy.¹Is C₁~ C₁₂Hydrocarbylene, each m is 0 or 1, each n is 0 or 1, each R²~ R⁴Is independently hydrogen or C₁~ C₁₈It is a hydrocarbyl, and L has the structure of the following equation.

<chemistry num="2"><img file="JP5147397B2_D0002.tif" /></chemistry>In the formula, each R⁵And R⁶Independently hydrogen, halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Hydrocarbyloxy, a halogen atom and an oxygen atom separated by two or more carbon atoms C₂~ C₁₂For example, halohydrocarbyloxy, z is 0 or 1, and Y has the structure of the following equation.

<chemistry num="3"><img file="JP5147397B2_D0003.tif" /></chemistry>In the formula, R⁷, R⁸And R⁹Are independently hydrogen and C₁~ C₁₂Hydrocarbyl, etc. In the last partial structure, R⁸And R⁹May be cis or trans-arranged for double bonds. In one embodiment, the sum of x is 4 or greater. As used herein, the term "hydrocarbyl", both in terms of terms and prefixes, refers to residues consisting only of carbon and hydrogen. The residue may be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated or unsaturated, or a combination thereof. However, as specified, the hydrocarbyl residue may contain a heteroatom in addition to the carbon and hydrogen atoms of the substituent. That is, the hydrocarbyl residue may contain a carbonyl group, an amino group, a hydroxyl group, a carboxylic acid group, a halogen atom, or the like, particularly when it is said to contain such a heteroatom, or is contained in the main chain of the hydrocarbyl residue. May contain a heteroatom.

In another embodiment, the bifunctional poly (arylene ether) has the structure of the following equation.

<chemistry num="4"><img file="JP5147397B2_D0004.tif" /></chemistry>During the ceremony, Q¹Is methyl and each Q²Are independently hydrogen or methyl, each R²Is independently hydrogen or methyl, R³And R⁴Is hydrogen and each R⁵And R⁶Independently hydrogen, halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Hydrocarbyloxy, a halogen atom and an oxygen atom separated by two or more carbon atoms C₂~ C₁₂For example, halohydrocarbyloxy, each x is 1 to about 100. In one embodiment, the sum of x is 4 or greater.

In another embodiment, the bifunctional poly (arylene ether) has the structure of the following equation.

<chemistry num="5"><img file="JP5147397B2_D0005.tif" /></chemistry>During the ceremony, Q¹Is methyl and each Q²Are independently hydrogen or methyl, each R²Is independently hydrogen or methyl, R³And R⁴Is hydrogen and each R⁵And R⁶Independently hydrogen, halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Hydrocarbyloxy, a halogen atom and an oxygen atom separated by two or more carbon atoms C₂~ C₁₂Halohydrocarbyloxy, etc., R⁸And R⁹Is independently hydrogen or C₁~ C₆For example, hydrocarbyl, each x is 1 to about 100.

In another embodiment, the bifunctional poly (arylene ether) has the structure of the following equation.

<chemistry num="6"><img file="JP5147397B2_D0006.tif" /></chemistry>In the equation, each x is from 1 to about 100 and z is 0 or 1.

As described above, bifunctional poly (arylene ether) can be produced by various synthetic methods. In one embodiment, the bifunctional poly (arylene ether) is the product of the following method. That is, monohydric phenol is oxidatively polymerized in the presence of a catalyst under conditions suitable for the formation of the corresponding poly (arylene ether) and the corresponding diphenoquinone, and the poly (arylene ether) and diphenoquinone are separated from the catalyst to form the poly (arylene ether). The diphenoquinone is equilibrated to form a poly with two terminal hydroxy groups (arylene ether), and the poly with two terminal hydroxy groups (arylene ether) is reacted with a sequestering agent to form a bifunctional poly (arylene). Ether) is formed. A specific example of the corresponding poly (arylene ether) is poly (2,6-dimethyl-1,4-phenylene ether) produced by oxidative polymerization of 2,6-dimethylphenol. Specific examples of the corresponding diphenoquinone are 3,3', 5,5'-tetramethyl-4,4'-diphenoquinone formed by oxidation of 2,6-dimethylphenol.

In another embodiment, the difunctional poly (arylene ether) is the product of an oxidative copolymerization of monohydric phenol and divalent phenol. Suitable monohydric phenols generally have the structure of:

<chemistry num="7"><img file="JP5147397B2_D0007.tif" /></chemistry>During the ceremony, Q¹Is halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydrocarbyloxy, a halogen atom and an oxygen atom separated by two or more carbon atoms C₂~ C₁₂Halohydrocarbyloxy, etc., Q²Is hydrogen, halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydrocarbyloxy, a halogen atom and an oxygen atom separated by two or more carbon atoms C₂~ C₁₂For example, halohydrocarbyloxy. Many specific monovalent phenols are described, for example, in Hay's US Pat. No. 3,306,875. In one embodiment, the monohydric phenol is 2,6-dimethylphenol, 2,3,6-trimethylphenol or a mixture thereof.

Suitable divalent phenols generally have the structure of:

<chemistry num="8"><img file="JP5147397B2_D0008.tif" /></chemistry>In the formula, each R⁵And R⁶Independently hydrogen, halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Hydrocarbyloxy, a halogen atom and an oxygen atom separated by two or more carbon atoms C₂~ C₁₂For example, halohydrocarbyloxy, z is 0 or 1, and Y has the structure of the following equation.

<chemistry num="9"><img file="JP5147397B2_D0009.tif" /></chemistry>In the formula, R⁷, R⁸And R⁹Are independently hydrogen and C₁~ C₁₂Hydrocarbyl, etc. Specific examples of suitable dihydric phenols include, for example, 3,3', 5,5'-tetramethyl-4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) methane, 1,1-. Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (ie "bisphenol A" or "BPA"), 2,2-bis (4-hydroxyphenyl) butane, 2,2- Bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -n-butane, bis (4-hydroxyphenyl) phenylmethane, 2, 2-Bis (4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, bis (hydroxyaryl) alkane, for example 2,2-bis (4-hydroxy-) 2,6-Dimethylphenyl) Propane ("Tetramethylbisphenol A" or "TMBPA"), 2,2-Bis (4-Hydroxy-3-bromophenyl) Propane, 1,1-Bis (4-Hydroxyphenyl) Cyclo Examples include pentan, bis (hydroxyaryl) cycloalkane, such as 1,1-bis (4-hydroxyphenyl) cyclohexane and the like and mixtures thereof.

In one embodiment, the bifunctional poly (allylen ether) is produced by a method comprising isolation by devolatilization extrusion. Suitable procedures for devolatilization extrusion are described, for example, in Braat et al., US Pat. No. 6,384,176. In another embodiment, the bifunctional poly (arylene ether) has a residual terminal-OH group of less than 100 ppm. According to the production method described in the following examples, a bifunctional poly (arylene ether) resin satisfying this condition can be produced. According to the production method described in the following examples, a bifunctional poly (arylene ether) resin satisfying these conditions can be produced.

In one embodiment, the bifunctional poly (arylene ether) has a number average molecular weight of about 1000 to about 10,000 atomic mass units (AMU), whereas the bifunctional poly (arylene ether) with a number average molecular weight less than about 500 AMU is 10. Less than 25% by weight of bifunctional poly (arylene ether) with a number average molecular weight of less than about 1000 AMU. In another embodiment, the bifunctional poly (allylene ether) has a number average molecular weight of about 10,000 AMU or more, whereas the bifunctional poly (allylene ether) with a number average molecular weight of less than about 500 AMU is less than 2% by weight and the number. Bifunctional polys (arylene ethers) with an average molecular weight of less than about 1000 AMU are less than 5% by weight, preferably less than 1% by weight.

In one embodiment, the bifunctional poly (arylene ether) has the following properties: having a number average molecular weight of less than 5000 AMU, less than 1% by weight of polymer with a molecular weight of less than 500 AMU, and 5 weight of polymer with a molecular weight of more than 30,000 AMU. Less than%, having a "vinyl" (ie, carbon-carbon double bond) functional group of 200 micromoles / g or more, acid value less than 1 milligram KOH / g, decomposition initiation temperature 450 It may have one or more properties of being greater than ° C. A bifunctional poly (arylene ether) resin satisfying these conditions can be produced by the production method described in the following examples.

The curable composition comprises from about 5 to about 90 parts by weight of the bifunctional poly (arylene ether) per 100 parts by weight of the total of the bifunctional poly (arylene ether) and the olefinically unsaturated monomer. Within the above range, the amount of the bifunctional poly (arylene ether) resin can be specifically about 10 parts by weight or more, more specifically about 15 parts by weight or more. Similarly, within the above range, the amount of the bifunctional poly (arylene ether) resin is specifically about 80 parts by weight or less, more specifically about 60 parts by weight or less, and more specifically about 50 parts by weight. It can be:

In addition to the bifunctional poly (allylen ether), the curable composition comprises an olefinically unsaturated monomer. In the present invention, an olefinically unsaturated monomer is defined as a polymerizable monomer containing a carbon-carbon double bond. Suitable olefinically unsaturated monomers include, for example, alkenyl aromatic monomers, allylic monomers, acryloyl monomers, vinyl ethers, maleimides and the like, and mixtures thereof.

The alkenyl aromatic monomer has the following formula.

<chemistry num="10"><img file="JP5147397B2_D0010.tif" /></chemistry>In the formula, each R¹⁰Is independently hydrogen or C₁~ C₁₈Hydrocarbyl, each R¹¹Is independently halogen, C₁~ C₁₂Alkyl, C₁~ C₁₂Alkoxy or C₆~ C₁₈It is aryl, q is 1 to 4, and r is 0 to 5. Unspecified positions on the aromatic ring are replaced by hydrogen atoms. Suitable alkenyl aromatic monomers include, for example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t. -Butylstyrene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, having 1-5 halogen substituents on the aromatic ring There are styrene and the like and combinations thereof. In one embodiment, the alkenyl aromatic monomer is styrene.

The olefinically unsaturated monomer may be an allyl-based monomer. The allyl monomer is one or more allyls (-CH).₂-CH = CH₂) Is an organic compound containing a group. In one embodiment, the allyl monomer has two or more allyl groups. In another embodiment, the allyl monomer has 3 or more allyl groups. Suitable allyl-based monomers include, for example, diallyl phthalate, diallyl isophthalate, triallyl melitate, triallyl mecinate, triallylbenzene, triallyl cyanurate, triallyl isocyanurate, mixtures thereof, and partial polymerization products produced from these. There are things, etc., as well as mixtures thereof.

The olefinically unsaturated monomer may be an acryloyl monomer. The acryloyl monomer is a compound containing one or more acryloyl groups having the structure of the following formula.

<chemistry num="11"><img file="JP5147397B2_D0011.tif" /></chemistry>In the formula, R¹²~ R¹⁴Are independently hydrogen and C₁~ C₁₂Hydrocarbyl, C₂~ C₁₈Hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, thiocarboxylic acid and the like. In one embodiment, the acryloyl monomer has two or more acryloyl groups. In another embodiment, the acryloyl monomer has three or more acryloyl groups. Suitable acryloyl monomers include, for example, trimethylolpropantri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di. (Meta) acrylate, cyclohexanedimethanol di (meth) acrylate, butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, There are methacryloxypropyltrimethoxysilane, ethoxylated (2) bisphenol A di (meth) acrylate and the like and mixtures thereof. The number after the word ethoxylation refers to the average number of ethoxy groups in the ethoxylate chain bound to each oxygen of bisphenol A. In one embodiment, the acryloyl monomer has two or more acryloyl groups. In another embodiment, the acryloyl monomer has three or more acryloyl groups.

The olefinically unsaturated monomer may be a vinyl ether. Vinyl ether is one or more vinyl ethers (-O-CH = CH)₂) A compound containing a group. In one embodiment, the vinyl ether contains two or more vinyl ether groups. In another embodiment, the vinyl ether contains 3 or more vinyl ether groups. Suitable vinyl ethers include, for example, 1,2-ethylene glycol divinyl ether, 1,3-propanediol divinyl ether, 1,4-butanediol divinyl ether, triethylene glycol divinyl ether, and 1,4-cyclohexanedimethanol divinyl ether. , Ethyl vinyl ether, n-butyl vinyl ether, lauryl vinyl ether, 2-chloroethyl vinyl ether and the like and mixtures thereof.

The olefinically unsaturated monomer may be maleimide. Maleimide is a compound containing one or more of the structures of the following formula.

<chemistry num="12"><img file="JP5147397B2_D0012.tif" /></chemistry>Suitable maleimides include, for example, N-phenylmaleimide, 1,4-phenylene-bis-methylene-α, α'-bismaleimide, 2,2-bis (4-phenoxyphenyl) -N, N'-bismaleimide. , N, N'-phenylene bismaleimide, N, N'-hexamethylene bismaleimide, NN'-diphenylmethane bismaleimide, N, N'-oxy-di-p-phenylene bismaleimide, N, N'-4,4 -Benzenephenone bismaleimide, N, N -p-diphenylsulfone bismaleimide, N, N -(3,3-dimethyl) methylene-di-p-phenylene bismaleimide, poly (phenylmethylene) polymaleimide, bis (4-Phenyloxyphenyl) sulfone-N, N'-bismaleimide, 1,4-bis (4-phenoxy) benzene-N, N'-bismaleimide, 1,3-bis (4-phenoxy) benzene-N, There are N'-bismaleimide, 1,3-bis (3-phenoxy) benzene-N, N'-bismaleimide and the like and mixtures thereof.

The composition generally comprises from about 10 to about 95 parts by weight of the olefinically unsaturated monomer per 100 parts by weight of the total of the bifunctional poly (arylene ether) and the olefinically unsaturated monomer. Within the above range, the amount of the olefinically unsaturated monomer can be specifically about 20 parts by weight or more, more specifically about 30 parts by weight or more. Similarly, within the above range, the amount of the olefinically unsaturated monomer can be specifically about 80 parts by weight or less, more specifically about 60 parts by weight or less.

Since a curable composition is defined as containing multiple components, each component is chemically distinguishable, especially if a single compound can satisfy the definition of two or more components.

The curable composition may further contain a curing initiator, as appropriate. Curing initiators, also referred to as curing catalysts, are well known in the art and can polymerize, cure or crosslink a number of thermoplastic and thermosetting materials such as unsaturated polyesters, vinyl esters and allyl thermosetting materials. Can be used to get started. Non-limiting examples of curing initiators are those described in US Pat. No. 5407972 by Smith et al. And No. 5218030 by Katayose et al. Examples of the curing initiator include compounds capable of generating free radicals at high temperatures. Such curing initiators may include both peroxy and non-peroxy radical initiators. Examples of useful peroxy initiators include, for example, benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, t-butyl peroctate, 2, 5-Dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexa-3-in, di-t-butyl peroxide, t-butylcumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di (t-butylperoxy) isophthalate, t-butyl Peroxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) There are peroxides, trimethylsilylphenyl triphenylsilyl peroxides and the like and mixtures thereof. Suitable non-peroxy initiators include, for example, 2,3-dimethyl-2,3-diphenylbutane, 2,3-trimethylsilyloxy-2, There are 3-diphenylbutane and the like and mixtures thereof. Further, examples of the curing initiator for the unsaturated group of the thermosetting material include a compound capable of initiating anionic polymerization of the unsaturated component. Examples of such anionic polymerization initiators include sodium amide (NaNH).₂) And lithium diethylamide (LiN (C)₂H₅)₂) Like alkali metal amides, C₁~ C₁₀Alkoxide alkali metals and ammonium salts, alkali metals and ammonium hydroxides, alkali metal cyanides, organometallic compounds such as alkyllithium compounds (n-butyllithium), Grignard reagents such as phenylmagnesium bromide, and these. There is a combination of. In one embodiment, the curing initiator consists of t-butyl peroxybenzoate or dicumyl peroxide. The curing initiator can accelerate curing at a temperature of about 0 to about 200 ° C.

If present, the curing initiator can be used in an amount of about 0.1 to about 5 parts by weight per 100 parts by weight of the bifunctional poly (arylene ether) and the olefinically unsaturated monomer. Within the above range, the amount of the curing initiator can be specifically about 0.5 parts by weight or more, more specifically about 1 part by weight or more. Similarly, within the above range, the amount of the curing initiator can be specifically about 4 parts by weight or less, more specifically about 3 parts by weight or less. The amount of the curing initiator can also be expressed in micromolar units per gram of resin, in which case the "resin" is a bifunctional poly (allylen ether) and an olefinically unsaturated monomer. In this embodiment, the amount of curing initiator is about 100 micromoles or more per gram of resin.

The curable composition may further contain a curing inhibitor as appropriate. Suitable curing inhibitors include, for example, diazoaminobenzene, phenylacetylene, sym-trinitrobenzene, p-benzoquinone, acetaldehyde, aniline condensate, N, N'-dibutyl-o-phenylenediamine, N-butyl-p-. Aminophenol, 2,4,6-triphenylphenoxyl, pyrogallol, catechol, hydroquinone, monoalkylhydroquinone, p-methoxyphenol, t-butylhydroquinone, C₁~ C₆-Alkyl substituted catechol, dialkylhydroquinone, 2,4,6-dichloronitrophenol, halogen-ortho-nitrophenol, alkoxyhydroquinone, phenol and catechol mono-and di-and polysulfide, quinone thiol, oxime and hydrazone, phenothiazine, There are dialkylhydroxylamines and the like, as well as combinations thereof. Suitable curing inhibitors also include unblocked poly (arylene ether) (ie, poly with a free hydroxyl group (arylene ether)). In one embodiment, the curing inhibitor consists of benzoquinone, hydroquinone, 4-t-butylcatechol or a mixture thereof.

When a curing inhibitor is present, it can be used in an amount of about 0.005 to about 1 part by weight per 100 parts by weight of the total of the bifunctional poly (arylene ether) and the olefinically unsaturated monomer. Within the above range, the amount of the curing inhibitor can be specifically about 0.05 parts by weight or more, more specifically about 0.1 parts by weight or more. Similarly, within the above range, the amount of the curing inhibitor can be specifically about 0.5 parts by weight or less, more specifically about 0.3 parts by weight or less. In one embodiment, the amount of curing inhibitor can be expressed in micromolar units per gram of resin, where the "resin" is a bifunctional poly (allylen ether) and an olefinically unsaturated monomer. In this embodiment, the amount of curing inhibitor can be about 50 micromoles or more per gram of resin.

The composition may optionally further contain an adhesion promoter to improve the adhesion between the cured composition and the metal substrate, particularly the lead frame used in the semiconductor package. Suitable adhesion promoters include metal (meth) acrylates, combinations of aromatic epoxy compounds and aromatic amines, vinyl aromatic compounds and α, β-unsaturated cyclic anhydride copolymers, partial (meth) acrylates. There are epoxy compounds and the like and mixtures thereof. The metal (meth) acrylate can have the structure of the following equation.

<chemistry num="13"><img file="JP5147397B2_D0013.tif" /></chemistry>In the formula, each R¹⁵Is independently hydrogen or methyl, M is a metal of groups 1 to 15 of the periodic table, and p is an integer of 1 to 6 depending on the valence of M. In one embodiment, M is a Group 1, 2, 12 or 13 metal of the Periodic Table. In one embodiment, M is zinc and p is 2. As a combination of the aromatic epoxy compound and the aromatic amine, the aromatic epoxy compound is a bisphenol-based epoxy resin (for example, bisphenol A glycidyl ether, bisphenol F glycidyl ether, 4,4'-diphenol glycidyl ether, 2,2', 6,6'-Tetramethyl-4,4'-diphenol glycidyl ether), novolak type epoxy resin, etc. or a mixture thereof, and the aromatic amine is a monocyclic aromatic amine (eg, aniline, toluidine), simple. Cyclic aromatic diamine (eg, diaminobenzene, xylylene diamine), monocyclic aromatic amino alcohol (eg, aminophenol), polycyclic aromatic diamine (eg, diaminodiphenylmethane, tetramethyldiaminodiphenylmethane and diaminodiphenylsulfone) ), Polycyclic aromatic amines, etc., or copolymers that are mixtures thereof. The aromatic epoxy compound and the aromatic amine can be used in a ratio of an epoxy group to an amino hydrogen atom having a molar ratio of about 1: 2 to about 2: 1. When the adhesion accelerator consists of a copolymer of a vinyl aromatic compound and an α, β-unsaturated cyclic anhydride, the vinyl aromatic compound may have the structure described above with respect to the alkenyl aromatic monomer, and the α, β-unsaturated cyclic anhydride may be used. Anhydride is C₄~ C₁₂Cyclic anhydride may be used. Preferred copolymers of vinyl aromatic compounds and α, β-unsaturated cyclic anhydrides are styrene and maleic anhydride having a styrene content of about 50 to about 95% by weight and a maleic anhydride content of about 5 to about 50% by weight. It is a copolymer of. When the adhesion accelerator consists of a partially (meth) acrylated epoxy compound, the compound is a reaction product of the above aromatic epoxy compound with acrylic acid or methacrylic acid, and about 5 to about 95% of the epoxy groups react. Then, a (meth) acrylate ester group is formed. If present, the adhesion accelerator can be used in an amount of about 0.1 to about 20 parts by weight per 100 parts by weight of the total of the bifunctional poly (arylene ether) and the olefinically unsaturated monomer. Within the above range, the amount of the adhesion accelerator may be specifically about 1 part by weight or more, and more specifically about 3 parts by weight or more. Similarly, within the above range, the amount of the adhesion accelerator may be specifically about 15 parts by weight or less, more specifically about 10 parts by weight or less.

In one embodiment, the curable composition comprises a functionalized poly (arylene ether), an olefinically unsaturated monomer, and a metal (meth) acrylate, a combination of an aromatic epoxy compound and an aromatic amine, a vinyl aromatic compound. It consists of a copolymer of α, β-unsaturated cyclic anhydride, a partially (meth) acrylated epoxy compound and an adhesion promoter selected from mixtures thereof. In this embodiment, the functionalized poly (allylene ether) can be a closed poly (allylene ether) or a ring functionalized poly (allylene ether) as defined below, respectively.

The functionalized poly (allylene ether) may be a closed poly (allylene ether). In the present invention, the blocked poly (arylene ether) is 50% or more, preferably 75% or more, more preferably 90% or more, and even more preferably 90% or more of the free hydroxyl groups present in the corresponding unsealed poly (arylene ether). 95% or more, more preferably 99% or more, is defined as poly (arylene ether) functionalized by reaction with a sequestering agent.

The blockade poly (arylene ether) can be expressed by the structure of the following equation.

Q (JK)_yIn the formula, Q is a monovalent, divalent or polyvalent phenol residue, preferably a monovalent or divalent phenol residue, more preferably a monovalent phenol residue, y is 1 to 100, and J is the following. It consists of a repeating structural unit having a formula.

<chemistry num="14"><img file="JP5147397B2_D0014.tif" /></chemistry>In the equation, m is 1 to about 200, preferably 2 to about 200, and R²And R⁴Are independent halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Hydrocarbon Oxy, halogen atom and oxygen atom separated by two or more carbon atoms C₂~ C₁₂Halo hydrocarbons such as oxy, R¹And R³Are independently hydrogen, halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Hydrocarbon Oxy, halogen atom and oxygen atom separated by two or more carbon atoms C₂~ C₁₂Halo hydrocarbons such as oxy. Further, K in the formula is a sequestering group generated by the reaction of the phenolic hydroxyl group on the poly (arylene ether) with the sequestering agent. The resulting blocking group is as follows.

<chemistry num="15"><img file="JP5147397B2_D0015.tif" /></chemistry>In the formula, R⁵Is C₁~ C₁₂Alkyl, etc., R⁶~ R⁸Are independently hydrogen and C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₆~ C₁₈Aryl, C₇~ C₁₈Alkylated aryl, C₇~ C₁₈Aryl-substituted alkyl, C₂~ C₁₂Alkoxycarbonyl, C₇~ C₁₈Aryloxycarbonyl, C₇~ C₁₈Alkylated aryloxycarbonyl, C₇~ C₁₈Aryl-substituted alkoxycarbonyls, nitriles, formyls, carboxylates, imitates, thiocarboxylates, etc., R⁹~ R¹³Are independently hydrogen, halogen, and C₁~ C₁₂It is alkyl, hydroxy, amino, etc., and Y is a divalent group as shown in the following formula.

<chemistry num="16"><img file="JP5147397B2_D0016.tif" /></chemistry>In the formula, R¹⁴And R¹⁵Are independently hydrogen and C₁~ C₁₂Alkyl and the like.

In one embodiment, Q is a phenolic residue, including polyfunctional phenol, which has a structural group of the following equation:

<chemistry num="17"><img file="JP5147397B2_D0017.tif" /></chemistry>In the formula, R¹~ R⁴Are independently hydrogen, halogen, first or second C₁~ C₁₂Alkyl, C₁~ C₁₂Alkenyl, C₁~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydrocarbon Oxy, halogen atom and oxygen atom separated by two or more carbon atoms C₁~ C₁₂Halo hydrocarbons such as oxy, where X is hydrogen and C₁~ C₁₂Alkyl, C₆~ C₁₈Aryl, C₇~ C₁₈Alkylated aryl, C₇~ C₁₈Any of the aryl-substituted alkyls or above hydrocarbon groups contains one or more substituents such as carboxylic acids, aldehydes, alcohols, amino groups, and X yields various bis- or higher polyphenols. As described above, sulfur, sulfonyl, sulfyl, oxygen and other similar bridging groups having a valence of 2 or more may be used, and y and n are independently 1 to about 100, preferably 1 to 3, and more preferably about. It is 1 to 2, and y = n in a preferred embodiment. Q may also be a residue of diphenols such as 2,2', 6,6'-tetramethyl-4,4'-diphenols or bisphenol A.

In one embodiment, the closed poly (allylen ether) is produced by sealing the poly (allylene ether) which is essentially composed of a polymerization product of one or more monovalent phenols having the structure of the following formula.

<chemistry num="18"><img file="JP5147397B2_D0018.tif" /></chemistry>In the formula, R¹~ R⁴Are independently hydrogen, halogen, first or second C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₂~ C₁₂Alkyne, C₁~ C₁₂Aminoalkyl, C₁~ C₁₂Hydroxyalkyl, phenyl, C₁~ C₁₂Haloalkyl, C₁~ C₁₂Hydrocarbon Oxy, halogen atom and oxygen atom separated by two or more carbon atoms C₂~ C₁₂Halo hydrocarbons such as oxy. Suitable monovalent phenols include those described in Hay's US Pat. No. 3,306,875, and highly preferred monovalent phenols include 2,6-dimethylphenol and 2,3,6-trimethylphenol. The poly (arylene ether) may be a copolymer of two or more monohydric phenols such as 2,6-dimethylphenol and 2,3,6-trimethylphenol. In another embodiment, the sealing poly (allylene ether) comprises the bifunctionalized poly (allylene ether) described above.

In a preferred embodiment, the sealing poly (arylene ether) comprises one or more sealing groups of the structure of the following formula.

<chemistry num="19"><img file="JP5147397B2_D0019.tif" /></chemistry>In the formula, R⁶~ R⁸Are independently hydrogen and C₁~ C₁₂Alkyl, C₂~ C₁₂Alkenyl, C₆~ C₁₈Aryl, C₇~ C₁₈Alkylated aryl, C₇~ C₁₈Aryl-substituted alkyl, C₂~ C₁₂Alkoxycarbonyl, C₇~ C₁₈Aryloxycarbonyl, C₇~ C₁₈Alkylated aryloxycarbonyl, C₇~ C₁₈Aryl-substituted alkoxycarbonyls, nitriles, formyls, carboxylates, imitates, thiocarboxylates and the like. A highly preferred blocking group is acrylate (R).⁶= R⁷= R⁸= Hydrogen) and methacrylate (R)⁶= Methyl, R⁷= R⁸= Hydrogen).

The functionalized poly (arylene ether) may be a ring-functionalized poly (arylene ether). In the present invention, a ring-functionalized poly (arylene ether) is defined as a poly (arylene ether) containing a repeating structural unit of the following equation.

<chemistry num="20"><img file="JP5147397B2_D0020.tif" /></chemistry>In the formula, each L¹~ L⁴Is independently a hydrogen, alkenyl group or alkynyl group, and the alkenyl group is represented by the following formula.

<chemistry num="21"><img file="JP5147397B2_D0021.tif" /></chemistry>In the formula, L⁵~ L⁷Is independently hydrogen or methyl, and a is an integer from 1 to 4. The alkynyl group in the above formula is represented by the following formula.

<chemistry num="22"><img file="JP5147397B2_D0022.tif" /></chemistry>In the formula, L⁸Is hydrogen, methyl or ethyl, and b is an integer from 1 to 4. All L in the ring-functionalized poly (allylen ether)¹~ L⁴About 0.02 to about 25 mol% of the substituents are alkenyl and / or alkynyl groups. Within the above range, it will be preferable that about 0.1 mol% or more, more preferably about 0.5 mol% or more is an alkenyl and / or alkynyl group. Similarly, within the above range, it may be preferable that about 15 mol% or less, more preferably about 10 mol% or less is an alkenyl and / or alkynyl group.

The ring-functionalized poly (arylene ether) can be produced by a known method. For example, an unfunctionalized poly (allylen ether) such as poly (2,6-dimethyl-1,4-phenylene ether) is metallized with a reagent such as n-butyllithium and then halogenated such as allyl bromide. It may react with alkynyl halides and / or alkynyl halides such as propargyl bromide. This method and other methods for producing ring-functionalized poly (arylene ether) resins are described, for example, in Katayose et al., US Pat. No. 4,923,932.

There are no particular restrictions on the molecular weight or intrinsic viscosity of the functionalized poly (arylene ether). In one embodiment, the composition may comprise a functionalized poly (allylene ether) having a number average molecular weight of about 10,000 atomic weight units (AMU) or less, preferably about 5000 AMU or less, more preferably about 3000 AMU or less. .. Such functionalized poly (allylene ether) will be useful in the production and processing of compositions due to its low viscosity.

In another embodiment, the composition is measured in chloroform at 25 ° C. from about 0.08 to about 0.30 dl / g (dL / g), preferably from about 0.12 to about 0.30 dL / g, more preferably from about 0.15 to. functional Capo having an intrinsic viscosity of about 0.25 dL / g may include Li (arylene ether). In general, the intrinsic viscosity of a functionalized poly (allylene ether) is not very different from the intrinsic viscosity of the corresponding unfunctionalized poly (allylene ether). Specifically, the intrinsic viscosity of the functionalized poly (allylene ether) is generally within 10% of the intrinsic viscosity of the unfunctionalized poly (allylene ether). These intrinsic viscosities roughly correspond to a number average molecular weight of about 5000 to about 25000 AMU. Within the above range, a number average molecular weight of about 8000 AMU or higher would be preferred. Also, a number average molecular weight of about 10,000 AMU or higher would be more preferred. Further, within the above range, a number average molecular weight of about 20000 AMU or less would be preferable. Such functionalized poly (allylene ether) provides a composition with the desired balanced toughness and processability. Obviously, it is also conceivable to use a blend of two or more functionalized polys (arylene ethers) with different molecular weights and intrinsic viscosities.

Methods for making functionalized poly (allylene ether), as well as another suitable functionalized poly (allylene ether) structure, are described in Yeager et al., US Patent Application Publication No. 2003-0096123.

When the composition comprises a functionalized poly (allylen ether), an olefinically unsaturated monomer and an adhesion enhancer, the functionalized poly (arylene ether) is a functionalized poly (arylene ether), an olefinically unsaturated monomer and an adhesion enhancer. It can be blended in an amount of about 1 to about 90 parts by weight per 100 parts by weight in total. Within the above range, the amount of the functionalized poly (arylene ether) is preferably about 5 parts by weight or more, more preferably about 10 parts by weight or more, and even more preferably about 15 parts by weight or more. Similarly, within the above range, functionalized poly (allylene ether) is preferably about 80 parts by weight or less, more preferably about 60 parts by weight or less, further preferably about 40 parts by weight or less, and further preferably about 30 parts by weight or less. ) Is used. Further, the composition may contain about 10 to about 95 parts by weight of the olefinically unsaturated monomer per 100 parts by weight of the total of the functionalized poly (arylene ether), the olefinically unsaturated monomer and the adhesion accelerator. Within the above range, the amount of the olefinically unsaturated monomer will be specifically about 20 parts by weight or more, more specifically about 30 parts by weight or more. Similarly, within the above range, the amount of the olefinically unsaturated monomer will be specifically about 90 parts by weight or less, more specifically about 80 parts by weight or less. Further, the composition may contain the adhesion accelerator in an amount of about 0.1 to about 30 parts by weight per 100 parts by weight of the functionalized poly (arylene ether), the olefinically unsaturated monomer and the adhesion accelerator in total. Within the above range, the amount of the adhesion promoter will be specifically about 1 part by weight or more, more specifically about 3 parts by weight or more, and even more specifically 5 parts by weight or more. Similarly, within the above range, the amount of the adhesion promoter will be specifically about 20 parts by weight or less, more specifically about 15 parts by weight or less.

One embodiment is a cured composition obtained by curing a curable composition composed of a functionalized poly (arylene ether), an olefinically unsaturated monomer and an adhesion accelerator. This cured composition can be used in the production of useful articles. One embodiment is an article comprising a cured composition and a metal substrate, wherein the curable composition is brought into contact with the metal substrate and cured to form an adhesive junction between the cured composition and the metal substrate. It is formed by doing. The metal substrate is made of, for example, copper foil.

The composition may further contain one or more fillers, including granular fillers and fibrous fillers, as appropriate. Examples of such fillers are well known in the art and are described in the Plastic Additives Handbook, 4^th Edition , R. Gachter and H. Muller (ed.), PP Klemchuck (co-ed.), Hanser Publishers, New York 1993, pp. 901-948. In the present invention, a granular filler is defined as a filler having an average aspect ratio of less than about 5: 1. Non-limiting examples of fillers are silica powders such as fused silica and crystalline silica, boron nitride powders and borosilicates for obtaining cured products with high thermal conductivity, low dielectric constant and low dielectric loss tangent. Acid powder, the above powder for high temperature conductivity and alumina and magnesium oxide (ie magnesia), as well as wollastonite including surface treated wollastonite, calcium sulfate (its anhydrous, semi-hydrated, dihydrated). Or trihydrate form), generally 98 +% CaCO₃Calcium carbonate, surface-treated calcium carbonate, including choke, limestone, marble and synthetic precipitated calcium carbonate, often in the form of crushed granules, including magnesium carbonate, iron oxide and other inorganic substances such as aluminosilicate. Has talc, including fibrous, baby-boomer, needle-like and lamellar talc, both hollow and solid glass spheres, and coupling agents such as usually silane coupling agents and / or conductive coatings. Surface-treated glass spheres containing, as well as kaolin and other kaolins, including various coatings known in the art to aid in dispersion and compatibility with hard, soft, calcined kaolin and thermosetting resins. Mica, slag and kasumi stone flashes, silicate spheres, smoke, senospheres, including mica surface-treated with aminosilane or acryloylsilane coating to impart good physical properties to metallized mica and compounded blends. , Philite, silicified and metallized aluminosilicates and other aluminosilicates (almospheres), natural silica sand, quartz, quartz rocks, pearlite, tripoly, diatomaceous soil, and those with various silane coatings. There are fillers such as synthetic silica.

In one embodiment, the granular filler is fused silica having an average particle size of about 1 to about 50 μm. A typical granular filler comprises a first molten silica having a median particle size of about 0.03 μm to less than 1 μm and a second molten silica having a median particle size of 1 μm or more and about 30 μm. Fused silica can have essentially spherical particles that are usually achieved by remelting. Within the above specific particle size range, the first molten silica may have a median particle size of specifically about 0.1 μm or more, specifically about 0.2 μm or more. Further, within the above particle size range, the first molten silica may have a median particle size of about 0.9 μm or less, more specifically, about 0.8 μm or less. Within the above specific particle size range, the second molten silica may have a median particle size of specifically about 2 μm or more, specifically about 4 μm or more. Further, within the above particle size range, the second molten silica may have a median particle size of about 25 μm or less, more specifically, about 20 μm or less. In one embodiment, the composition comprises a first molten silica and a second fused silica in a weight ratio of about 70:30 to about 99: 1, specifically about 80:20 to about 95: 5. ..

Fibrous fillers include inorganic short fibers, including processed mineral fibers such as those obtained from a blend of one or more aluminum silicates, aluminum oxide, magnesium oxide and calcium sulfate hemihydrates. is there. Further, among the fibrous fillers, there are single crystal fibers or "whiskers" containing silicon carbide, alumina, boron carbide, carbon, iron, nickel and copper. Further, the fibrous filler includes glass fibers such as E, A, C, ECR, R, S, D and NE glass and glass fibers for textiles such as quartz. Typical fibrous fillers include glass fibers having a diameter of about 5 to about 25 μm and a pre-compound length of about 0.5 to about 4 cm. Many other suitable fillers are described in Yeager et al., US Pat. No. 6,672,704.

While non-conductive fillers may be preferred for plastic encapsulation electronics, the composition can also be used in other applications where conductive fillers are desirable. For such applications, suitable conductive fillers include conductive carbon fibers such as graphite, conductive carbon black, single-walled carbon nanotubes and multi-walled carbon nanotubes, metal fibers, metal particles, and inherently conductive polymers. There are particles and the like, as well as mixtures thereof.

The formulation may also contain an adhesion enhancer to improve the adhesion of the thermosetting resin to the filler or external coating or substrate. It is also possible to treat the above-mentioned inorganic filler with an adhesion accelerator to improve adhesion. Adhesion promoters include chromium complexes, silanes, titanates, zircoamates, propylene maleic anhydride copolymers, reactive cellulose esters and the like. Some chromium complexes are sold by DuPont under the trademark VOLAN®. General structure (RO) for silane_(4-n)SiY_nHere, n = 1 to 3, R is an alkyl or aryl group, and Y is a reactive functional group capable of forming a bond with a polymer molecule. A particularly useful example of a coupling agent is structure (RO).₃It has SiY. Typical examples are vinyltriethoxysilane, vinyltris (2-methoxy) silane, phenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane. , Γ-Mercaptopropyltrimethoxysilane and the like. Silanes also include molecules lacking reactive functional groups, such as trimethoxyphenylsilane. Titanates developed by SJ Monte et al. (Ann.Chem.Tech Conf.SPI (1980), Ann.Tech Conf.Reinforced Plastics and Composite Inst.SPI 1979, Section 16E, New Orleans) and SJ Monte (Mod. Plastics Int., Vol. 14, No. 6, p. 2 (1984)). As zircoaluminate, Plastics by LB Cohen Some are described in Engineering, Vol. 39, No. 11, p. 29 (1983). The adhesion accelerator can be contained in the thermosetting resin itself or applied on any of the above fillers to improve the adhesion between the filler and the thermosetting resin. For example, such accelerators can be used to coat silicate fibers or fillers to improve resin matrix adhesion.

If present, the granular filler can be used in an amount of about 5 to about 95% by weight based on the total weight of the composition. Within the above range, the amount of the granular filler can be specifically about 20% by weight or more, more specifically about 40% by weight or more, and more specifically about 75% by weight or more. Similarly, within the above range, the amount of the granular filler can be specifically about 93% by weight or less, more specifically about 91% by weight or less.

If present, the fibrous filler can be used in an amount of about 2 to about 80% by weight based on the total weight of the composition. Within the above range, the amount of the fibrous filler can be specifically about 5% by weight or more, more specifically about 10% by weight or more, and more specifically about 15% by weight or more. Similarly, within the above range, the amount of the fibrous filler can be specifically about 60% by weight or less, more specifically about 40% by weight or less, and more specifically about 30% by weight or less.

The above-mentioned filler may be added to the thermosetting resin without any treatment, or may be added after surface treatment with a usual adhesion accelerator.

Curable compositions, as appropriate, further include, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, fluidity improvers, drip inhibitors, flame retardants, anti-adhesion. One or more known in the art such as agents, antistatic agents, flow promoters, processing aids, substrate adhesives, mold release agents, toughening agents, hyposhrinkants, stress relievers, etc. and combinations thereof. May contain the additive of. Those skilled in the art can select suitable additives and determine the appropriate amount without undue experimentation.

One advantage of the curable compositions of the present invention is their improved molding properties. For example, the curable composition may exhibit a spiral flow of about 50 cm or more as measured according to the procedure described below at a temperature of about 130 to about 180 ° C and a pressure of about 3 to about 7 MPa. ..

In one embodiment, the curable composition is an olefin consisting of a bifunctional poly (arylene ether) having an intrinsic viscosity of about 0.08 to about 0.25 dl / g at 25 ° C, an acryloyl monomer containing two or more acryloyl groups. Sexual unsaturated monomer, benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butylbenzene peroxide, t-butylperoctate, 2,5-dimethylhexane-2, 5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexa-3-in, di-t-butyl peroxide, t-butylcumyl peroxide, α, α'-bis ( t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di (t-butylperoxy) isophthalate, t-butylperoxybenzoate, 2,2- Bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilylphenyltriphenylsilyl Curing initiators selected from peroxides and mixtures thereof, as well as diazoaminobenzene, phenylacetylene, sym-trinitrobenzene, p-benzoquinone, acetaldehyde, aniline condensates, N, N'-dibutyl-o-phenylenediamine, N. -Butyl-p-aminophenol, 2,4,6-triphenylphenoxyl, pyrogallol, catechol, hydroquinone, monoalkylhydroquinone, p-methoxyphenol, t-butylhydroquinone, C₁~ C₆-Alkyl substituted catechol, 4-t-butyl catechol, dialkylhydroquinone, 2,4,6-dichloronitrophenol, halogen-ortho-nitrophenol, alkoxyhydroquinone, phenol and catechol mono-and di- and polysulfide, thiol of quinone , Oxime and hydrazone, phenothiazine, dialkylhydroxylamine, and curing inhibitors selected from mixtures thereof. Here, the bifunctionalized poly (arylene ether) has the structure of the following equation.

<chemistry num="23"><img file="JP5147397B2_D0023.tif" /></chemistry>During the ceremony, Q¹Is methyl and each Q²Are independently hydrogen or methyl, each R²Is independently hydrogen or methyl, R³And R⁴Is hydrogen and R⁸And R⁹Is independently hydrogen or C₁~ C₆It is hydrocarbyl, and each x is 1 to about 100.

In another embodiment, the curable composition is a bifunctional poly (arylene ether) having an intrinsic viscosity of about 0.08 to about 0.20 dl / g at 25 ° C., about 5 to about 90 parts by weight, about 5 to about 5 to. Approximately 90 parts by weight of trimethylol propantri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) Acrylic, cyclohexanedimethanol di (meth) acrylate, butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, methacryloxypropyl Trimethoxysilane, ethoxylated (2) bisphenol A di (meth) acrylate or acryloyl monomer selected from a mixture of two or more of the above acryloyl monomers, about 0.2 to about 5 parts by weight of benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone Peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butylbenzene hydroperoxide, t-butyl peroctate, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2, 5-Di (t-butylperoxy) -hexa-3-in, di-t-butyl peroxide, t-butylcumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2, 5-Dimethyl-2,5-di (t-butylperoxy) hexane, di (t-butylperoxy) isophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2- Bis (t-butylperoxy) octane, 2,5-dimethyl-2,A curing initiator selected from 5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilylphenyltriphenylsilyl peroxide and mixtures thereof, and about 0.005 to about 1 part by weight of diazoaminobenzene, phenylacetylene. , Sym-trinitrobenzene, p-benzoquinone, acetaldehyde, aniline condensate, N, N'-dibutyl-o-phenylenediamine, N-butyl-p-aminophenol, 2,4,6-triphenylphenoxyl, pyrogallol, Catecol, hydroquinone, monoalkyl hydroquinone, p-methoxyphenol, t-butyl hydroquinone, C₁~ C₆-Alkyl substituted catechol, 4-t-butyl catechol, dialkylhydroquinone, 2,4,6-dichloronitrophenol, halogen-ortho-nitrophenol, alkoxyhydroquinone, phenol and catechol mono-and di- and polysulfide, thiol of quinone , Oxime and hydrazone, phenothiazine, dialkylhydroxylamine, and a curing inhibitor selected from mixtures thereof, wherein the bifunctional poly (arylene ether) has the structure of the following formula.

<chemistry num="24"><img file="JP5147397B2_D0024.tif" /></chemistry>In the equation, each x is from 1 to about 50 and z is 0 or 1. In addition, all the above parts by weight are based on a total of 100 parts by weight of bifunctional poly (arylene ether) and acryloyl monomer.

Another embodiment comprises blending a bifunctional poly (allylen ether) having an intrinsic viscosity of about 0.05 to about 0.30 dl / g at 25 ° C with an olefinically unsaturated monomer to form a homogeneous blend. , A method of forming a curable composition.

One embodiment is a cured composition obtained by curing any of the above curable compositions. The term "curing" includes partial curing and complete curing. Since the components of the curable composition can react with each other during curing, it can be said that the curable composition is composed of reaction products of the components of the curable composition.

One advantage of this curable composition is that it exhibits excellent rigidity and impact strength after curing. For example, the cured composition can exhibit bending strength of about 90 MPa or more as measured according to ASTM D790. As another example, the cured composition may exhibit breaking energies of 0.8 J or greater as measured according to ASTM D790.

Another advantage of the curable composition is that it exhibits excellent dispersion of the poly (arylene ether) phase after curing. For example, the cured composition exhibits a domain size of a cured olefinically unsaturated monomer phase covered with poly (arylene ether) of about 50 nm to about 1 μm as determined by a transmission electron microscope. This high degree of poly (arylene ether) dispersion offers many property advantages, including improved uniformity of surface appearance.

Another embodiment is an article comprising any of the cured compositions. The curable composition is useful in the production of a wide range of articles and is particularly suitable for use as a sealing material for electronic devices.

The present invention is further illustrated in the following non-limiting examples.

<u style="single">Example 1</u> In this example, the preparation of the redistribution polyphenylene ether resin will be described. In a three-necked flask, poly (2,6-dimethyl-1,4-phenylene ether) (intrinsic viscosity = 0.46 dl / g (dL / g), 90 g (g)), toluene (260 (mL)) and bisphenol A (5.4g) was added. The reaction mixture was heated to 90 ° C to form a homogeneous solution. Benzoyl peroxide (5.4 g) was added little by little to this heated solution. After the addition was complete, the reaction was maintained at 90 ° C for about 2 hours. The solution was then cooled to room temperature and the product polyphenylene ether was precipitated from methanol. The resulting material contained 0.56 wt% hydroxyl groups (as -OH). Hydroxy terminal groups are derivatized with phosphorus reagents as described in KPChan, DSArgyropoulos, DMWhite, GW eager and ASHay, Macromolecules, 1994, Vol. 27, p. 6371 et seq.³¹Measured by quantification by PNMR.

<u style="single">Examples 2-9, Comparative Examples 1 and 2</u> Using the procedure of Example 1, several redistributed poly (arylene ether) resins were prepared by varying the intrinsic viscosity of the poly (arylene ether) starting material, the concentration of bisphenol A and the concentration of benzoyl peroxide. All reactions were carried out with a solid content of 25% by weight in toluene. One sample, Example 6, also used a modified finishing process. That is, the sample was refluxed with pyrrolidine to remove the benzoic acid ester group from the redistributed polyphenylene ether. After cooling the reaction mixture to room temperature, the product was precipitated by mixing 1 volume of the cooled reaction mixture with 2 volumes of methanol. The precipitate was filtered and washed with additional methanol. The hydroxyl group content was determined as described above. Intrinsic viscosity was measured at 25 ° C in chloroform. Number average molecular weight (M_n) And weight average molecular weight (M)_w) Are expressed in atomic mass units (AMU), but were determined by gel permeation chromatography using polystyrene standards. Functionality for each sample (d_f) Corresponds to the average number of hydroxyl groups per poly (arylene ether) chain and is calculated by the following equation.

d_f= ([OH] /17.01) × (M_n/10⁶) Here, [OH] is the hydroxyl content of polyphenylene ether expressed in parts per million, and M._nIs the number average molecular weight of polyphenylene ether expressed in atomic mass units. For comparison, unreacted starting polyphenylene ethers were also characterized (Comparative Examples 1 and 2).

Table 1 summarizes the reaction conditions and the results of determining the characteristics of the product.

<tables num="1"><img file="JP5147397B2_D0025.tif" /></tables>

<tables num="2"><img file="JP5147397B2_D0026.tif" /></tables>

<tables num="3"><img file="JP5147397B2_D0027.tif" /></tables><u style="single">Example 10</u> Starting materials include poly (2,6-dimethyl-1,4-phenylene ether) (PPE) with an intrinsic viscosity of 0.41 dL / g and a hydroxyl content of 0.65 wt%, 6 wt% bisphenol A (PPE standard) and Redistributed polyphenylene ethers were prepared using 6 wt% benzoyl peroxide (PPE standard) in the same manner as in Example 1. The reaction mixture was refluxed with pyrrolidine (2.4 times benzoyl peroxide at the molar level) to remove the benzoic acid ester group. The resulting redistribution PPE was sealed with methacrylate in a reaction with 362 g of redistribution PPE, 362 g of styrene, 5 g of dimethylaminopyridine and 65.2 g of methacrylic anhydride. This methacrylate-blocked polyphenylene ether product had a hydroxyl content below the detection limit of 15 parts per million by weight.

<u style="single">Example 11</u> Using the procedure described in Example 1, as starting materials, 450 g of poly (2,6-dimethyl-1,4-phenylene ether) with an intrinsic viscosity of 0.25 dL / g, 1170 mL of toluene, 18 g of bisphenol A and Redistributed polyphenylene ethers were prepared with 18 g of benzoyl peroxide. After 3 hours, 33 mL of pyrrolidine was added and the reaction mixture was refluxed for an additional 20 hours. The product was precipitated with methanol, filtered, washed and dried in a vacuum oven at 110 ° C. for 20 hours. The resulting redistributed polyphenylene ether was sealed with methacrylate in a reaction mixture containing 363.6 g of redistributed polyphenylene ether, 363.6 g of styrene, 5 g of dimethylaminopyridine and 43.47 g of methacrylic anhydride. The reaction mixture was maintained at 85 ° C. for 23 hours to give a methacrylate-sealed polyphenylene ether with a hydroxyl content of 90.9 parts by weight per million parts.

<u style="single">Examples 12 and 13, Comparative Examples 3 to 5</u> Five compositions were prepared, molded and tested for the effect of the structure of the sealing poly (allylen ether) on the shrinkage and appearance of the molded part. In Examples 12 and 13, polyphenylene ether (PPE-MA) with both ends sealed with methacrylate prepared by redistribution of polyphenylene ether having an intrinsic viscosity of 0.25 dL / g and subsequent sealing was used. This double-ended closed PPE-MA had an intrinsic viscosity of less than 0.25 dL / g. In Comparative Examples 3 and 4, polyphenylene ethers prepared from unsealed polyphenylene ethers having an intrinsic viscosity of about 0.40 dL / g and one end sealed with methacrylate were used. In Comparative Example 5, a polyphenylene ether having one end sealed with methacrylate, which was prepared from an unsealed polyphenylene ether having an intrinsic viscosity of about 0.12 dL / g, was used. To prepare a sample for testing, a methacrylate-sealed polyphenylene ether (PPE-MA) was mixed with styrene and the mixture was heated to 80 ° C to dissolve the polyphenylene ether. The mixture was then degassed in vacuum at 80 ° C to give a clear, bubble-free solution. Benzoyl peroxide was then added and the resulting mixture was injected into a flexbar mold preheated to 75 ° C. The filled mold was placed in a convection oven and then subjected to a heating profile of rising to 110 ° C and down to 45 ° C for about 3 hours. The molded part was visually inspected to see if the appearance and shrinkage of the part from the mold were uniform. The composition and results are summarized in Table 2. The results show that only Examples 12 and 13 prepared from polyphenylene ethers with low intrinsic viscosity and sealed with methacrylate at both ends showed good overall appearance, uniform shrinkage, and no cracks and bubbles. ing.

<tables num="4"><img file="JP5147397B2_D0028.tif" /></tables><u style="single">Example 14</u> In this example, the preparation of methacrylate-blocking poly (arylene ether) from redistribution poly (arylene ether) will be described. The redistribution poly (arylene ether) (100 g) prepared in the procedure of Example 1 was dissolved in toluene (300 mL). To the resulting solution was added 4-dimethylaminopyridine (2.68 g), triethylamine (6.68 g) and methacrylic anhydride (10.16 g). The reaction mixture was heated to 90 ° C and heated overnight. The reaction product methacrylate-blocking poly (allylen ether) was precipitated from methanol. This product contained 10 ppm of unblocked hydroxyl end groups.

<u style="single">Examples 15-21</u> Polyphenylene ethers with various degrees of functionality were prepared using seven polymerization reactions. In each case, the components of the reaction mixture are 2,6-xylenol (760.86 g), toluene (2512.87 g), cuprous bromide (CuBr, 6.1 g), di-t-butylethylenediamine (1.254 g), It was di-n-butylamine (7.803 g), dimethylbutylamine (26.52 g) and quaternary ammonium surfactant (0.77 g). All 2,6-xylenol was added at the beginning of the reaction. Samples were taken at the recorded reaction times, the product poly (allylen ether) was precipitated with methanol, dried and analyzed for molecular weight and hydroxyl end group content. In each case, the end point of the reaction time was determined by inactivating the reaction catalyst by adding an aqueous solution of nitrilotriacetic acid (NTA). That is, if the re-equilibration time is zero in Table 3, the NTA solution is quickly mixed with the reaction mixture and the resulting two-phase mixture is separated by centrifugation, effectively reducing the re-equilibration time to a few minutes. Limited. For longer rebalancing times, NTA solution was added, the entire two-phase mixture was stirred for a specific equilibration time, and then separated by centrifugation. The re-equilibration temperature was 60 ° C for all samples except Example 3, and the equilibration temperature for Example 3 was 60 ° C for the first 2 hours and 85 ° C for the last 2 hours.

Table 3 shows the hydroxyl content and number average molecular weight of poly (arylene ether) as a function of various oxygen flow rates, exotherm, reaction time, oxygen pressure and reequilibrium time. Table 1 summarizes the reaction conditions and the characteristics of poly (arylene ether). The results show that high oxygen flow and pressure provide the highest functionality of poly (allylene ether) after 1-2 hours of reequilibrium.

<tables num="5"><img file="JP5147397B2_D0029.tif" /></tables> In Example 21, the above reagents were added except that 64.75 g of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane (tetramethylbisphenol A, TMBPA) was gradually added throughout the reaction time. Was prepared using. The results in Table 2 show that the addition of TMBPA increased the functionality of the poly (allylen ether).

<tables num="6"><img file="JP5147397B2_D0030.tif" /></tables><u style="single">Example 22</u> In this example, the synthesis of bifunctional poly (arylene ether) by polymerization of 2,6-dimethylphenol in the presence of tetramethylbisphenol A will be described. Methyltrioctylammonium chloride in 180 mL of toluene, 5.0 g of tetramethylbisphenol A, 0.56 mL of toluene (ADOGEN® 464) 10 in a Morton flask equipped with an overhead stirrer, thermometer, addition funnel and oxygen inlet tube. % Solution, 13.2 mL amine solution in toluene (prepared by mixing 1 mL di-t-butylethylenediamine, 20 mL dimethylbutylamine, 5.3 mL dibutylamine and 61.4 mL toluene), 2,6- in 12 mL toluene A 50% solution of dimethylphenol and a 0.5 mL solution of copper bromide were charged. After vigorous stirring of the mixture, oxygen was aerated into the solution at a flow rate of approximately 0.4 standard cubic feet / hour (SCFH). A 50% solution of 2,6-dimethylphenol in 108 mL toluene was added dropwise via an addition funnel over a period of about 23 minutes. During this time, an ice water bath was used to maintain the reaction temperature at about 25 ° C.

When the addition was complete, the ice bath was removed and the reaction temperature was raised to about 35 ° C. This temperature was maintained for 15-20 minutes due to the exotherm of the reaction. When the temperature began to drop, the reaction was returned to 35 ° C using a heated water bath. After 1 hour at this temperature, the oxygen flow was stopped and the water bath was heated to 60 ° C. This temperature was maintained for an additional 60 minutes. The reaction was then stopped with 2 mL of acetic acid and allowed to cool to room temperature.

The product was isolated using methanol precipitation. After filtration and drying in a vacuum oven, 56.87 g of material was obtained. GPC analysis using polystyrene standards showed a number average molecular weight of 5334 AMU and a weight average molecular weight of 11217 AMU. This product had an average of 1.7 hydroxy groups per chain.

<u style="single">Example 23</u> In this example, the synthesis of double-ended blockade poly (arylene ether) will be described. The polymer prepared in 56 g of Example 22 was mixed with 270 mL of toluene, 8.7 mL of methacrylic anhydride and 0.9 g of 4-dimethylaminopyridine and heated to a temperature of approximately 80 ° C with vigorous stirring. After 3 hours at this temperature, the reaction mixture was cooled to room temperature and then the product was isolated using a methanol precipitate. After filtration, the product was dried in a vacuum oven.

<u style="single">Example 24, Comparative Examples 6-9</u> This example describes the preparation, molding and curing of curable compositions with varying intrinsic viscosity and methacrylate functionalization of poly (arylene ether), as well as post-curing characterization. Examples 24 and 7-9 were 14.5% by weight poly (arylene ether), 82% ethoxylated (2) bisphenol A dimethacrylate (obtained as Sartomer SR 348), 0.5% anti-curing agent t-butyl. It contained catechol and 3% dicumyl peroxide. Comparative Example 6 was similar, but did not contain poly (arylene ether) and contained 96.5% ethoxylated (2) bisphenol A dimethacrylate. The polys (arylene ethers) of Examples 24 and Comparative Examples 7 to 9 have an intrinsic viscosity (IV) of 0.12 or 0.30 dL / g and are unsealed (methacrylate functionality = 0) or one end is sealed. Was it (methacrylate functionality = 1) or both ends were closed (methacrylate functionality = 2). This double-ended blockade poly (allylen ether) was prepared by the method described in Examples 22 and 23.

In order to prepare a curable composition containing poly (arylene ether), first of all, a single phase mixture of poly (arylene ether), an inhibitor and a dimethacrylate monomer is suppressed with solid poly (arylene ether). The agent was obtained by stirring and mixing the agent into a liquid monomer at about 150 to about 170 ° C. After clarification of this mixture, it was cooled to below 130 ° C and dicumyl peroxide was added. The resulting agitated mixture was poured into a cold aluminum tray, where it was cooled to a Tuffy-like consistency. A sample of this material, a polished stainless steel tool, Viton for sealing the top and bottom and circular perimeters. It was compression molded into a circular disc measuring 4 inches in diameter x 1/8 inch thick using an O-ring (Pasadena, 160 ° C, 5 tons, 5 min). After removal, the disc was cured after 2 hours at 175 ° C in a convection oven. These discs were wet-cut into straight 3 "x 1/2" x 1/8 "studet using a diamond-coated aluminum blade of a tile saw. These specimens were then dried in a convection oven at 110 ° C. for 1 hour.

<u style="single">Bending test</u> Samples were tested at room temperature in a three-point bending test in accordance with ASTM D790 to obtain the "Bending Strength", "Bending Modulus", "Breaking Strain" and "Breaking Energy" values in Table 5 and also to ASTM D5045. The "critical stress expansion coefficient" in Table 5 was obtained by testing in a compliant 3-point bending test with a single-ended notch. The flexural modulus is the slope of the first part of the stress-strain curve, and the breaking energy is the area below that curve. 9-11 specimens were tested for each sample, and the uncertainty in Table 5 represents 1 standard deviation.

<u style="single">Transmission electron microscopy</u> The sample was subjected to an ultramicrotome at room temperature to obtain a thin section having a thickness of about 90 nm. Successive sections were floated on water in a diamond knife boat and collected on a standard 300 mesh Cu TEM grid. Micrographs were taken with a Philips CM100 transmission electron microscope operated at an acceleration voltage of 100 kilovolts. Gas phase ruthenium tetroxide staining preferentially darkens the PPO-rich phase and enhances the contrast of the TEM image.

The results shown in Table 5 show that low intrinsic viscosity bifunctional poly (arylene ether) produces high bending strength and breaking energy close to high intrinsic viscosity monofunctional poly (allylene ether), but low intrinsic viscosity bifunctionality. It shows that the poly (arylene ether) showed remarkably excellent flow characteristics. The micrographs shown in FIGS. 1 to 5 for Comparative Example 6, Comparative Example 7, Example 24, Comparative Example 8 and Comparative Example 9 are the cured samples corresponding to Example 24 (Fig. 3, 0.12IV double-ended closed PPE). However, as compared with Comparative Example 7 (one-sided closed PPE in FIG. 2, 0.12IV) or Comparative Example 9 (one-sided closed PPE in FIG. 5, 0.30), a cured olefinically unsaturated monomer phase covered with poly (allylen ether). It shows the fine dispersion of olefinic unsaturated monomer, and shows that the compatibility with the olefinically unsaturated monomer is remarkably high.

<tables num="7"><img file="JP5147397B2_D0031.tif" /></tables><u style="single">Examples 25 and 26, Comparative Examples 10-12</u> Five samples of various types of functionalized poly (arylene ether) resins were prepared. In Example 25, prepared by methacrylate blockade of dihydroxypoly (allylen ether) synthesized by copolymerization of 2,6-dimethylphenol and 2,2-bis (4-hydroxy-2,6-dimethylphenyl) propane (TMBPA). Difunctionalized poly (allylene ether) with both ends sealed with methacrylate was used. This bifunctional poly (allylen ether) had a number average molecular weight of 3111 AMU and a weight average molecular weight of 5838 AMU. In Example 26, bifunctionalization (sealed with methacrylate at both ends) prepared by methacrylate sealing of dihydroxypoly (allylen ether) synthesized by polymerization of 2,6-dimethylphenol followed by redistribution with bisphenol A and benzoyl peroxide. Poly (arylene ether) was used. This bifunctional poly (arylene ether) had a number average molecular weight of 5712 AMU and a weight average molecular weight of 16997 AMU. In Comparative Example 10, a monofunctionalized (one end sealed with methacrylate) poly (2,6-dimethyl-1,4-) having an intrinsic viscosity of about 0.30 dL / g, a number average molecular weight of 17814 AMU, and a weight average molecular weight of 37474 AMU. Phenylene ether) was used. In Comparative Example 11, a monofunctionalized (one end sealed with methacrylate) poly (2,6-dimethyl-1,4-) having an intrinsic viscosity of about 0.25 dL / g, a number average molecular weight of 12869 AMU, and a weight average molecular weight of 26300 AMU. Phenylene ether) was used. In Comparative Example 12, a monofunctionalized (one end sealed with methacrylate) poly (2,6-dimethyl-1,4-) having an intrinsic viscosity of about 0.12 dL / g, a number average molecular weight of 4176 AMU, and a weight average molecular weight of 7631 AMU. Phenylene ether) was used.

All curable compositions consisted of 85.57 parts by weight of molten silica, 1.245 parts by weight of Clariant OP1311 obtained as an organophosphate flame retardant, 0.20 parts by weight of carbon black pigment obtained as Cabot Black Pearls 120, and 0.063 parts by weight of curing inhibition. Agent 4-t-butylcatechol, ethoxylated (2) bisphenol A dimethacrylate obtained as 9.60 parts by weight of Saltomer SR348, 1.694 parts by weight of functionalized poly (allylen ether), 0.85 parts by weight of poly (styrene-maleic anhydride) It consisted of a copolymer, 0.40 parts by weight of the release agent stearate and 0.378 parts by weight of the curing initiator t-butylperoxybenzoate.

It was prepared as described under the curable composition. A slurry was formed by mixing functionalized poly (arylene ether), acryloyl monomer and a curing inhibitor. The slurry was heated to 170 ° C. for about 13 minutes with stirring in a 250 mL beaker, at which point a styrene-maleic anhydride copolymer was added and heating was continued for an additional 2 minutes to give a clear solution. The solution was cooled to about 130 ° C. and other soluble components were added except for the initiator. After further cooling to 90 ° C, the curing initiator was added with sufficient mixing, and then all the remaining components were added and mixed. The composition was compounded by feeding into a Brabender mixer equipped with "roller" blades and operating at 60 rpm. The mixer was maintained at 80 ° C to soften the composition and promote wetting of the filler. The total compounding time was about 5 minutes. The compounded composition was cooled and stored in an airtight container until use.

Spiral flow was measured at 150 ° C. and 6.89 MPa according to SEMI G11-88 Recommended practice for ram follower gel time and spiral flow of thermal setting molding compounds. Bending strength, flexural modulus and bending elongation to break were measured at 23 ° C in accordance with ASTM D790.

The moisture absorption rate was measured according to the modified version of SEMI G66-96 "Test Method for the measurement of water absorption characteristics for semiconductor plastic molding compounds". This hygroscopicity property was determined by measuring the net weight gain of the sample condition adjusted for 168 hours at 85 ° C. and 85% relative humidity. The equipment used for this test was from an environmental chamber maintained at 85 ° C / 85% RH, a chemical balance capable of an accuracy of ± 0.0001 g, an oven capable of maintaining 110 ± 3 ° C, and oven drying. Holds a dryer to hold the sample being cooled, a "wet box" to hold the sample being cooled from the humidity condition control (a dryer with desiccant removed and water added), and a sample being dried in the oven and adjusted to the humidity condition. Included a cage.

Samples are sampled by a standard transfer molding process to prepare "Izod" specimens, i.e. using a 63.5 mm x 12.7 mm x 3.2 mm (2.5 × 0.5 × 1/8 ) mold cavity. Prepared. The dimensions of these samples differ from the SEMI standard to facilitate molding (SEMI recommends the use of 50 mm x 1 mm discs). Four or more test pieces were prepared for one compound. These samples were cured after 2 hours at 175 ° C.

To determine the reference "dry" weight, the post-molded hardened specimen was dried in an oven at 110 ° C. for 1 hour. The sample was then removed from the oven and placed in a dryer to cool to room temperature. This cooled sample was weighed approximately 0.0001 g using a chemical balance. This weight is the dry weight of the sample W₁Is.

After weighing to dry, the sample was placed in an environmental chamber maintained at 85 ° C / 85% RH for 168 hours (1 week). At the end of this conditioning period, the sample was removed from the environmental chamber and placed in a "wet box" to prevent loss of moisture during cooling and weighing. The samples were taken out of the box one by one when weighing. All the condensed moisture was wiped off with a lint-free cloth or the like. Next, the test piece was weighed again at approximately 0.0001 g, and the weight after adjusting the humidity state was W.₂And said.

The hygroscopicity was calculated by the following formula.

<maths num="1"><img file="JP5147397B2_D0032.tif" /></maths> Jetting behavior was investigated using defective filling injected into a standard 4-cavity tool designed to form a test piece for the Izod test. I shot a 12g shot into the tool and paid attention to the behavior of the flow head. Materials with smooth flow and no or few signs of finger-like jets were considered no jetting. Jetting was qualitatively graded from scale 0 (no jetting) to 5 (terrible jetting).

Coefficient of thermal expansion (CTE) and glass transition (T) using thermomechanical analysis_g)It was determined. The procedure outlined in SEMI G13-88 was used. A sample that was molded and cured with a size of 3 mm or more was cut to a size of approximately 3 mm x 3 mm x 3 mm, and attention was paid to the measurement direction (flow direction, vertical to flow surface, etc.).

An initial force of 0.05 Newton was used. The measurement was performed at 100 ml / min in a nitrogen atmosphere. The heating program was as follows. Equilibrated at 1:25 ° C, 2: 1min isothermal, Heat up to 250 ° C at 3: 5 ° C / min, 4: 1min isothermal, Cool to 0 ° C at 5: 5 ° C / min, Equilibrated at 6: 0 ° C, 7: 1min isothermal, The temperature rises to 250 ° C at 8: 5 ° C / min.

CTE and T using a second heating cycle_gWas calculated.

The composition and results are shown in Table 6. The results were reduced (improved) in Examples 25 and 26 with the low molecular weight single-ended blockade poly (allylene ether) compared to Comparative Examples 10 and 11 with the high molecular weight single-ended blockade poly (allylene ether). It is shown to show jetting and increased spiral flow. This improvement is the moisture absorption rate, CTE or T_gAchieved without lowering the value.

Considering the results of these experiments together, the use of low molecular weight double-ended blockade poly (allylen ether) has traditionally achieved high spiral flow, low jetting, compatibility with high olefinically unsaturated monomers and low shrinkage. It is clear that combinations that were not available will be possible. Changes in either the molecular weight or the degree of functionalization impair one or more of these properties.

<tables num="8"><img file="JP5147397B2_D0033.tif" /></tables><u style="single">Examples 27 to 30, Comparative Example 13</u> This example demonstrates the effectiveness of the adhesion promoter in improving the adhesion of the composition to the copper foil. Five compositions were prepared with different types and amounts of adhesion promoters. In Comparative Example 13, no adhesion promoter was used. Example 27 contained zinc acrylate obtained as SR705 from 1.17 wt% Sartomer. Example 28 contained a styrene-maleic anhydride copolymer obtained as SMA EF30 from 1.17 wt% Sartomer. Example 29 contained a partially acrylated epoxy oligomer obtained as EBECRYL® 3605 from 1.17 wt% Surface Specialties / UCB. Example 30 is 1.125% by weight of Resolution, respectively. It contained a 3: 1 weight / weight mixture of diglycidyl ether and methylene dianiline of bisphenol A obtained from Chemicals and Aldrich. All of these compositions are Denka essentially spherical molten silica obtained from Aldrich and silane treated silica prepared from methacryloxypropyltrimethoxysilane, colorants (carbon black or dye), release waxes (LICOWAX (LICOWAX). Registered trademarks) OP, Clariant), flame retardants (MELAPUR® 200 from Ciba Specialty Chemicals or OP1311 from Clariant), dicumyl peroxide initiators, 4-t-butylcatechol inhibitors, acryloyl monomer ethoxylated bisphenol A dimethacrylates It contained (as SR348 from Sartomer), as well as a poly (2,6-dimethyl-1,4-phenylene ether) resin (PPO-MA) with an intrinsic viscosity of about 0.3 dL / g, one end sealed with methacrylate. The total composition is shown in Table 7.

The curable composition was prepared using the following general procedure. Monomers, inhibitors and powdered PPO-MA (sieved down to -35 mesh) were mixed together to form a slurry. The mixture in the 250 mL beaker thus obtained was placed in an oil bath maintained at about 170 ° C. The mixture was mixed with a stirrer immersed in this slurry. The mixture was heated for approximately 15 minutes with stirring until the solution became clear. Adhesive promoters such as zinc acrylate, partially acrylated epoxy oligomers and styrene-maleic anhydride were added near the end of the dissolution process. The resulting mixture was removed from the oil bath and cooled to room temperature in air.

The resulting resin mixture was compounded with other components (treated silica, flame retardant, wax, initiator, carbon black pigment) using a Brabender mixer. The resin-filler mixture was fed to a Brabender mixer equipped with "roller" blades and operated at 60 rpm. The mixer was maintained at 80 ° C to soften / liquefy the resin and wet the filler. A total mixing time of about 5 minutes was used. The compound was then removed from the mixer, cooled and stored in an airtight container.

Adhesion to copper substrates was measured according to SEMI G69-0996 "Test Method for measurement of adhesive strength between leadframes and molding compounds". Using the "tensile" method, a 5 mil thick copper substrate was transfer molded at 155 ° C (175 ° C in Example 30) into blocks of 2.8 mm thick molding compound. The copper substrate used was Furukawa's EFTEC 64T 1 / 2H grade. Adhesive area (copper triangle part molded in molding compound) is about 15.2 mm including both sides²Met. The molded test piece was annealed / then cured at 175 ° C for 2 hours. Prior to the test, the condition was adjusted at room temperature for approximately 24 hours. Adhesion between the molded compound and copper was tested by pulling a copper "tab" from the molded compound using an Instron tensile tester at a speed of 2 mm / min. The peak load is recorded and shown as adhesive strength. The measured peak load is shown in pounds, where 1 pound has a nominal bond area of 15.2 mm.²Corresponds to the interfacial shear strength of 0.297 MPa. Mean and standard deviations for tab tensile adhesion values were determined for 6 or more samples per composition.

The results listed in Table 7 show that each adhesion accelerator is effective in substantially increasing the tabbing tensile adhesion between the cured composition and the copper foil.

<tables num="9"><img file="JP5147397B2_D0034.tif" /></tables> Although the present invention has been described above with respect to preferred embodiments, it will be apparent to those skilled in the art that various modifications are possible within the technical scope of the invention and that equivalents can replace the elements of the invention. Let's do it. Also, many modifications can be made without departing from the essential scope of the invention in order to adapt the particular material and situation to the teachings of the invention. Therefore, the present invention is not limited to the specified embodiments disclosed that are considered to be the best embodiments of the invention, but includes all embodiments that fall within the scope of the claims.

The disclosures of cited patents, patent applications and other documents are incorporated herein by reference.<u style="single">The features of the present invention are as follows.</u><u style="single">A curable composition comprising a bifunctional poly (allylen ether) having an intrinsic viscosity of about 0.05 to about 0.30 dl / g at 1.25 ° C and an olefinically unsaturated monomer.</u><u style="single">2. The curable composition of 1 above, wherein the bifunctional poly (arylene ether) has the structure of the following formula.</u><chemistry num="25"><img file="JP5147397B2_D0035.tif" /></chemistry><u style="single">In the formula, each Q</u>^{<u style="single">1</u>}<u style="single">Is independently halogen, first or second C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyne, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Aminoalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydroxyalkyl, phenyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydrocarbyloxy and halogen atoms and oxygen atoms separated by two or more carbon atoms C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Selected from halohydrocarbyloxy, each Q</u>^{<u style="single">2</u>}<u style="single">Independently hydrogen, halogen, first or second C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyne, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Aminoalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydroxyalkyl, phenyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydrocarbyloxy and halogen atoms and oxygen atoms separated by two or more carbon atoms C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Selected from halohydrocarbyloxy, each x is 1 to about 100 independently, each R</u>^{<u style="single">1</u>}<u style="single">Is C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydrocarbylene, each n being 0 or 1, each R</u>^{<u style="single">2</u>}<u style="single">~ R</u>^{<u style="single">4</u>}<u style="single">Is independently hydrogen or C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">18</u>}<u style="single">It is a hydrocarbyl, and L has the structure of the following equation.</u><chemistry num="26"><img file="JP5147397B2_D0036.tif" /></chemistry><u style="single">In the formula, each R</u>^{<u style="single">5</u>}<u style="single">And R</u>^{<u style="single">6</u>}<u style="single">Independently hydrogen, halogen, first or second C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyne, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Aminoalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydroxyalkyl, phenyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydrocarbyloxy and halogen atoms and oxygen atoms separated by two or more carbon atoms C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Selected from halohydrocarbyloxy, z is 0 or 1 and Y has a structure selected from:</u><chemistry num="27"><img file="JP5147397B2_D0037.tif" /></chemistry><u style="single">In the formula, each R</u>^{<u style="single">7</u>}<u style="single">, R</u>^{<u style="single">8</u>}<u style="single">And R</u>^{<u style="single">9</u>}<u style="single">Independently hydrogen and C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Selected from hydrocarbyl.</u><u style="single">3. The curable composition according to 1 above, wherein the bifunctionalized poly (arylene ether) has the structure of the following formula.</u><chemistry num="28"><img file="JP5147397B2_D0038.tif" /></chemistry><u style="single">During the ceremony, Q</u>^{<u style="single">1</u>}<u style="single">Is methyl and each Q</u>^{<u style="single">2</u>}<u style="single">Are independently hydrogen or methyl, each R</u>^{<u style="single">2</u>}<u style="single">Is independently hydrogen or methyl, R</u>^{<u style="single">3</u>}<u style="single">And R</u>^{<u style="single">4</u>}<u style="single">Is hydrogen and each R</u>^{<u style="single">5</u>}<u style="single">And R</u>^{<u style="single">6</u>}<u style="single">Independently hydrogen, halogen, first or second C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyne, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Aminoalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydroxyalkyl, phenyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydrocarbyloxy and halogen atoms and oxygen atoms separated by two or more carbon atoms C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Selected from halohydrocarbyloxy,</u><u style="single">Each x is 1 to about 100.</u><u style="single">Four. Bifunctional poly (allylen ether),</u><u style="single"> Catalyst under conditions suitable for the formation of the corresponding poly (allylen ether) and the corresponding diphenoquinone</u><u style="single">Oxidative polymerization of monovalent phenol in the presence</u><u style="single"> Separation of poly (allylen ether) and diphenoquinone from the catalyst</u><u style="single"> Equilibrium poly (arylene ether) and diphenoquinone with two terminal hydroxy groups</u><u style="single">Form poly (allylene ether) with</u><u style="single"> A poly (arylene ether) having two terminal hydroxy groups is reacted with a sequestering agent to form two</u><u style="single">Form functionalized poly (allylen ether)</u><u style="single">The curable composition of 3 above, which is the product of the process comprising the above.</u><u style="single">5. The curable composition according to 1 above, wherein the bifunctionalized poly (arylene ether) has the structure of the following formula.</u><chemistry num="29"><img file="JP5147397B2_D0039.tif" /></chemistry><u style="single">During the ceremony, Q</u>^{<u style="single">1</u>}<u style="single">Is methyl and each Q</u>^{<u style="single">2</u>}<u style="single">Are independently hydrogen or methyl, each R</u>^{<u style="single">2</u>}<u style="single">Is independently hydrogen or methyl, R</u>^{<u style="single">3</u>}<u style="single">And R</u>^{<u style="single">4</u>}<u style="single">Is hydrogen and each R</u>^{<u style="single">5</u>}<u style="single">And R</u>^{<u style="single">6</u>}<u style="single">Independently hydrogen, halogen, first or second C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyne, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Aminoalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydroxyalkyl, phenyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydrocarbyloxy and halogen atoms and oxygen atoms separated by two or more carbon atoms C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Selected from halohydrocarbyloxy, R</u>^{<u style="single">8</u>}<u style="single">And R</u>^{<u style="single">9</u>}<u style="single">Is independently hydrogen or C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">It is hydrocarbyl, and each x is 1 to about 100.</u><u style="single">6. The curable composition according to 1 above, wherein the bifunctionalized poly (arylene ether) has the structure of the following formula.</u><chemistry num="30"><img file="JP5147397B2_D0040.tif" /></chemistry><u style="single">In the equation, each x is from 1 to about 100 and z is 0 or 1.</u><u style="single">7. The curable composition of 6 above, wherein the difunctionalized poly (allylen ether) is the product of an oxidative copolymerization of monohydric phenol and divalent phenol.</u><u style="single">8. The monovalent phenol is selected from 2,6-dimethylphenol, 2,3,6-trimethylphenol and mixtures thereof, and the divalent phenol is 3,3', 5,5'-tetramethyl-4,4'. -Biphenol, 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -n-butane, bis (4) -Hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy) -2,6-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxy) The curable composition according to 7 above, which is selected from phenyl) cyclohexane and a mixture thereof.</u><u style="single">9. The curable composition of 1 above, wherein the bifunctional poly (arylene ether) has an intrinsic viscosity of about 0.08 to about 0.20 dl / g.</u><u style="single">10. The curable composition of 1 above, wherein the bifunctional poly (allylen ether) is isolated by devolatilization extrusion.</u><u style="single">11. Bifunctional poly (arylene ether) with a number average molecular weight of less than 500 AMU is less than 10% by weight, and bifunctional poly (arylene ether) with a number average molecular weight of less than 1000 AMU is less than 25% by weight. The curable composition according to 1 above, wherein the bifunctionalized poly (arylene ether) has a number average molecular weight of about 1000 to about 10000 atomic mass units (AMU).</u><u style="single">12. Bifunctional poly (arylene ether) with a number average molecular weight of less than 500 AMU is less than 2% by weight, and bifunctional poly (arylene ether) with a number average molecular weight of less than 1000 AMU is less than 5% by weight. The curable composition according to 1 above, wherein the bifunctionalized poly (arylene ether) has a number average molecular weight of 10000 AMU or more.</u><u style="single">13. The curable composition according to 1 above, which comprises about 5 to about 90 parts by weight of the bifunctional poly (arylene ether) and about 5 to about 90 parts by weight of the bifunctional poly (arylene ether) per 100 parts by weight of the total of the olefinically unsaturated monomer.</u><u style="single">14. The curable composition according to 1 above, wherein the olefinically unsaturated monomer is selected from an alkenyl aromatic monomer, an allylic monomer, an acryloyl monomer, a vinyl ether, a maleimide, and a mixture thereof.</u><u style="single">15. The curable composition of 1 above, wherein the olefinically unsaturated monomer comprises an acryloyl monomer having two or more acryloyl groups.</u><u style="single">16. The olefinic unsaturated monomer is trimethylpropantri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di. (Meta) acrylate, cyclohexanedimethanol di (meth) acrylate, butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, The curable composition according to 1 above, which comprises a methacryloxypropyltrimethoxysilane, an ethoxylated (2) bisphenol A di (meth) acrylate, and an acryloyl monomer selected from a mixture thereof.</u><u style="single">17. The curable composition of 1 above, which comprises from about 10 to about 95 parts by weight of the olefinically unsaturated monomer per 100 parts by weight of the total of the bifunctional poly (arylene ether) and the olefinically unsaturated monomer.</u><u style="single">18. The curable composition of 1 above, further comprising a curing initiator.</u><u style="single">19. The curable composition of 1 above, further comprising a curing inhibitor.</u><u style="single">20. In addition, metal (meth) acrylates, combinations of aromatic epoxy compounds and aromatic amines, copolymers of vinyl aromatic compounds with α, β-unsaturated cyclic anhydrides, partial (meth) acrylated epoxy compounds, And the curable composition of 1 above, which comprises an adhesion promoter selected from a mixture thereof.</u><u style="single">21. The above 20 curable compositions, wherein the adhesion promoter comprises a styrene-maleic anhydride copolymer.</u><u style="single">22. The above 20 curable compositions containing about 0.1 to about 20 parts by weight of an adhesion promoter per 100 parts by weight of a total of bifunctional poly (arylene ether) and olefinically unsaturated monomer.</u><u style="single">23. Further, the curable composition of 1 above, further comprising a filler of about 2 to about 95% by weight based on the total weight of the composition.</u><u style="single">24. In addition, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, fluidity improvers, drip inhibitors, flame retardants, anti-adhesive agents, antistatic agents, flow promoters. The curable composition according to 1 above, which comprises an agent, a processing aid, a substrate adhesive, a mold release agent, a toughening agent, a low shrinkage agent, a stress relieving agent, and an additive selected from a combination thereof.</u><u style="single">25. The curable composition of 1 above, which has a spiral flow of about 50 cm or more as measured at a temperature of about 130 to about 180 ° C and a pressure of about 3 to about 7 MPa.</u><u style="single">With a bifunctional poly (arylene ether) having the following structure, which has an intrinsic viscosity of about 0.08 to about 0.25 dl / g at 26.25 ° C,</u><u style="single"> An olefinically unsaturated monomer composed of an acryloyl monomer containing two or more acryloyl groups,</u><u style="single"> Benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butylbenzene peroxide, t-butylperoctate, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-Dimethyl-2,5-di (t-butylperoxy) -hexa-3-in, di-t-butyl peroxide, t-butylcumyl peroxide, α, α'-bis (t-butylperoxy- m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di (t-butylperoxy) isophthalate, t-butylperoxybenzoate, 2,2-bis (t-butyl) Peroxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilylphenyltriphenylsilyl peroxide and mixtures thereof Curing initiator selected from</u><u style="single"> Diazoaminobenzene, phenylacetylene, sym-trinitrobenzene, p-benzoquinone, acetaldehyde, aniline condensate, N, N'-dibutyl-o-phenylenediamine, N-butyl-p-aminophenol, 2,4,6-tri Phenylphenoxyl, pyrogallol, catechol, hydroquinone, monoalkylhydroquinone, p-methoxyphenol, t-butylhydroquinone, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">-Alkyl substituted catechol, 4-t-butyl catechol, dialkylhydroquinone, 2,4,6-dichloronitrophenol, halogen-ortho-nitrophenol, alkoxyhydroquinone, phenol and catechol mono-and di- and polysulfide, thiol of quinone , Oxime and hydrazone, phenothiazine, dialkylhydroxylamine, and curing inhibitors selected from mixtures thereof.</u><u style="single">A curable composition comprising.</u><chemistry num="31"><img file="JP5147397B2_D0041.tif" /></chemistry><u style="single">During the ceremony, Q</u>^{<u style="single">1</u>}<u style="single">Is methyl and each Q</u>^{<u style="single">2</u>}<u style="single">Are independently hydrogen or methyl, each R</u>^{<u style="single">2</u>}<u style="single">Is independently hydrogen or methyl, R</u>^{<u style="single">3</u>}<u style="single">And R</u>^{<u style="single">4</u>}<u style="single">Is hydrogen and each R</u>^{<u style="single">5</u>}<u style="single">And R</u>^{<u style="single">6</u>}<u style="single">Independently hydrogen, halogen, first or second C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkenyl, C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Alkyne, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Aminoalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydroxyalkyl, phenyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Haloalkyl, C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Hydrocarbyloxy and halogen atoms and oxygen atoms separated by two or more carbon atoms C</u>_{<u style="single">2</u>}<u style="single">~ C</u>_{<u style="single">12</u>}<u style="single">Selected from halohydrocarbyloxy, R</u>^{<u style="single">8</u>}<u style="single">And R</u>^{<u style="single">9</u>}<u style="single">Is independently hydrogen or C</u>_{<u style="single">1</u>}<u style="single">~ C</u>_{<u style="single">6</u>}<u style="single">It is hydrocarbyl, and each x is 1 to about 100.</u><u style="single">27. About 5 to about 90 parts by weight of difunctional poly (allylene ether) with the following structure having an intrinsic viscosity of about 0.08 to about 0.20 dl / g at 25 ° C.</u><u style="single"> Approximately 5 to 90 parts by weight of trimethylol propantri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (Meta) acrylate, cyclohexanedimethanol di (meth) acrylate, butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, Acryloyl monomer selected from methacryloxypropyltrimethoxysilane, ethoxylated (2) bisphenol A di (meth) acrylate and mixtures thereof, and</u><u style="single">Approximately 0.2 to 5 parts by weight of benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butylbenzene peroxide, t-butylperoctate, 2,5-dimethyl Hexa-3-in, di-t-butyl peroxide, t-butyl cumyl peroxide, α, α, hexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexa-3-in -Bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di (t-butylperoxy) isophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilyl A curing initiator selected from phenyltriphenylsilyl peroxide and mixtures thereof,</u><u style="single"> About 0.005 to about 1 part by weight of diazoaminobenzene, phenylacetylene, sym-trinitrobenzene, p-benzoquinone, acetaldehyde, aniline condensate, N, N'-dibutyl-o-phenylenediamine, N-butyl-p-amino Phenol, 2,4,6-triphenylphenoxyl, pyrogallol, catechol, hydroquinone, monoalkylhydroquinone, p-methoxyphenol, t-butylhydroquinone, C1-C6-alkyl substituted catechol, 4-t-butylcatechol, dialkylhydroquinone , 2,4,6-dichloronitrophenol, halogen-ortho-nitrophenol, alkoxyhydroquinone, mono- and di- and polysulfides of phenols and catechols, thiols of quinones, oximes and hydrazone, phenothilines, dialkylhydroxylamines, and their With a hardening inhibitor selected from the mixture</u><u style="single">A curable composition that is based on a total of 100 parts by weight of bifunctional poly (arylene ether) and acryloyl monomer.</u><chemistry num="32"><img file="JP5147397B2_D0042.tif" /></chemistry><u style="single">In the equation, each x is from 1 to about 50 and z is 0 or 1.</u><u style="single">28.z is 1, the acryloyl monomer is ethoxylated (2) bisphenol A di (meth) acrylate, the curing initiator is dicumyl peroxide, and the curing inhibitor is t-butylcatechol. Curable composition.</u><u style="single">29. With functionalized poly (allylen ether),</u><u style="single">With olefinically unsaturated monomers</u><u style="single">Metal (meth) acrylates, combinations of aromatic epoxy compounds and aromatic amines, copolymers of vinyl aromatic compounds with α, β-unsaturated cyclic anhydrides, partially (meth) acrylated epoxy compounds, and mixtures thereof. With adhesion promoters to choose from</u><u style="single">A curable composition comprising.</u><u style="single">Curing comprising blending a bifunctional poly (allylen ether) having an intrinsic viscosity of about 0.05 to about 0.30 dl / g at 30.25 ° C with an olefinically unsaturated monomer to form a homogeneous blend. A method of forming a sex composition.</u><u style="single">31. A cured composition containing a reaction product obtained by curing the curable composition of 1 above.</u><u style="single">32. The above 31 cured compositions showing bending strength of about 90 MPa or more as measured in accordance with ASTM D790.</u><u style="single">33. The above 31 cured compositions showing breaking energy of 0.8 J or higher as measured according to ASTM D790.</u><u style="single">34. The cured composition of 31 above, which exhibits a poly (arylene ether) dispersed phase particle size of about 50 nm to about 1 μm.</u><u style="single">35. An article comprising the above 31 cured compositions.</u><u style="single">36. A cured composition containing a reaction product obtained by curing the above 26 curable compositions.</u><u style="single">37. An article comprising the above 36 cured compositions.</u><u style="single">38. A cured composition containing a reaction product obtained by curing the above 27 curable composition.</u><u style="single">39. An article comprising the above 38 cured compositions.</u><u style="single">40. A cured composition containing a reaction product obtained by curing the above 29 curable compositions.</u><u style="single">41. An article comprising the above 40 cured compositions.</u><u style="single">42. The 41 articles above, further comprising a metal substrate and formed by contacting and curing the curable composition with the metal substrate.</u>

<figref num="1">FIG. 1 is a transmission electron micrograph corresponding to Comparative Example 6.</figref><figref num="2">FIG. 2 is a transmission electron micrograph corresponding to Comparative Example 7.</figref><figref num="3">FIG. 3 is a transmission electron micrograph corresponding to Example 24.</figref><figref num="4">FIG. 4 is a transmission electron micrograph corresponding to Comparative Example 8.</figref><figref num="5">FIG. 5 is a transmission electron micrograph corresponding to Comparative Example 9.</figref>