JP2002284825A - Resin composition for laminate and laminate prepared by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a free-radically polymerizable resin composition which, when cured, gives a laminate exhibiting a high toughness and a low thermal expansion and capable of enduring precision working, such as drilling, at a high temperature. SOLUTION: This resin composition contains (a) a free-radically polymerizable resin, (b) a free-radically polymerizable monomer, and (c) fine polymer particles having hydroxyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for manufacturing a laminate for a printed wiring board, particularly a laminate manufactured by a continuous method, and having good drilling property and low thermal expansion property. The present invention relates to a resin composition for a laminate and a laminate manufactured using the same.

[0002]

2. Description of the Related Art Radical polymerizable resins such as vinyl esters and unsaturated polyesters have a good balance of workability and curability during molding, and a good balance of mechanical, chemical and electrical properties of cured products, and are used in various fields. It is used. In recent years, attention has been paid to the excellent electrical properties of these resins, and many applications in electrical and electronic related fields such as laminates have been seen. As for the laminated board, for example, a laminated board obtained by impregnating a base material with a resin composition containing a liquid vinyl ester resin containing a vinyl ester and a radical polymerizable monomer and a filler and curing the resin is disclosed in −
29548.

[0003]

However, the laminates manufactured by the conventional method have the disadvantages that they have a large coefficient of thermal expansion and poor drill workability when processing the laminates. Regarding this point, for example, in the technology described in the above publication, attempts have been made to solve these problems by increasing the amount of filler. However, even if this method can reduce the coefficient of thermal expansion and improve the drill workability, there are disadvantages such as a decrease in the strength of the laminate and a deterioration in chemical resistance, and materials that can be used practically Hard to say. As another method, attempts have been made to solve the above problem by dispersing acrylic polymer fine particles in a thermosetting resin composition (Japanese Patent Laid-Open No. 10-36).
463). However, according to this method, although a required low coefficient of thermal expansion is obtained, it is hard to say that sufficient performance is obtained in terms of drill workability. Therefore, a material sufficient to solve the above problem has not yet been obtained. More recently,
With the demand for finer processing of laminates, higher levels of workability than before, such as workability with small-diameter drills, are required from the material side. It is strongly desired.

[0004]

Means for Solving the Problems The present inventors have responded to the above-mentioned demand for fine processing of a laminated board, and have provided a resin composition for a laminated board which gives a cured product excellent drilling workability. As a result of intensive research to develop a laminated board using the above, it has been found that the above-mentioned problems can be solved by using a resin composition in which specific polymer fine particles are dispersed in a conventionally used resin composition, and the present invention has been achieved. It was completed. That is, the present invention provides (1) a resin composition for a laminate comprising (1) a radical polymerizable resin (a), a radical polymerizable monomer (b) and polymer fine particles (c) having a hydroxyl group, and (2) a polymer having a hydroxyl group. The resin composition for a laminate according to (1), wherein the fine particles (c) are multilayer polymer fine particles, and (3) a polymer fine particle having a hydroxyl group (c).
Is a multilayered polymer fine particle having a hydroxyl group in the outermost layer, (1) the resin composition for a laminate, (4) the thickness of the outermost layer of the hydroxyl group-containing polymer fine particle (c) is based on the particle radius. (2) or (3), wherein the equivalent of the hydroxyl group present in the hydroxyl group-containing layer of the polymer fine particles (c) having a hydroxyl group is 0.1 to 300 mgKOH / g. The resin composition for a laminate according to any one of (1) to (4), and (6) the resin composition according to any one of (1) to (5), further comprising an inorganic filler (d). Resin composition for laminate, (7) inorganic filler (d)
The resin composition for a laminate according to (6), wherein the compounding ratio of the resin composition is from 5 to 250 parts by weight based on 100 parts by weight of the resin composed of (a), (b) and (c), (8) (a), The cured product of the resin composition comprising (b) and (c) has a glass transition temperature of 120 ° C. or higher and a fracture toughness of 0.7 MNm.
^3/2 or more, wherein the resin composition for a laminate according to any one of (1) to (5) is impregnated with the resin composition for a laminate according to any one of (9) to (8). (1) to (8), on a surface layer of a laminate obtained by curing the cured substrate and a glass fiber woven fabric impregnated with the resin composition according to any one of (1) to (8). A composite laminate obtained by laminating and curing a glass fiber nonwoven fabric impregnated with the resin composition according to any one of the above, as an inner layer.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As the radical weight resin (a) used in the present invention, a general-purpose radical curable resin can be used, but when a laminate is made of a compound having high heat resistance, chemical resistance and compound. Since appropriate fluidity is required,
Among them, the use of vinyl ester or unsaturated polyester is preferred. The vinyl ester can be obtained by reacting a compound having one or more functional epoxy groups in one molecule with an unsaturated monobasic acid. Compounds having one or more functional epoxy groups in the molecule are disclosed in
No. 0-110948, bisphenol type epoxy resins represented by bisphenol A type and bisphenol F type and their halides, novolak type epoxy resins represented by phenol novolak and cresol novolak, aliphatic epoxy Resin, amine-type epoxy resin, copolymerization-type epoxy resin, alicyclic epoxy resin, and epoxy in the molecule of glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4- (meth) acryloxymethylcyclohexene oxide, etc. Compounds having a group and a (meth) acrylic double bond are exemplified. Among them, a bisphenol A type epoxy resin and a halide thereof are preferable examples.

As unsaturated monobasic acids, in addition to unsaturated monocarboxylic acids such as (meth) acrylic acid, polybasic anhydrides and at least one hydroxyl group and (meth) acrylic unsaturated group in one molecule are used. And a reaction product of a compound having the same. Examples of the polybasic acid anhydride used in the above reaction include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and aliphatic and aromatic dicarboxylic anhydrides such as hexahydrophthalic anhydride. . Examples of the compound having at least one hydroxyl group and a (meth) acrylic unsaturated group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate Glycerin di (meth) acrylate, a reaction product of (meth) acrylic acid and a polyhydric alcohol, and the like. Among these, (meth) acrylic acid is particularly preferred. The reaction between the epoxy group and the unsaturated monobasic acid can be carried out under known conditions. That is, tertiary amines such as dimethylbenzylamine,
The desired vinyl ester can be obtained by reacting at a reaction temperature of 80 to 150 ° C. for about 1 to 10 hours using a phosphine such as triphenylphosphine as a catalyst.

The unsaturated polyester is synthesized by condensation of an α, β-olefinic unsaturated dicarboxylic acid and glycol. In the synthesis of the polyester, in addition to these two components, a saturated dicarboxylic acid, an aromatic dicarboxylic acid, or dicyclopentadiene that reacts with the dicarboxylic acid can be used in combination. Examples of α, β-olefinically unsaturated dicarboxylic acids include, for example, maleic acid,
Fumaric acid, itaconic acid, citraconic acid and anhydrides of these dicarboxylic acids. Examples of these dicarboxylic acids used in combination with the α, β-olefinically unsaturated dicarboxylic acids include, for example, adipic acid, sebacic acid, succinic acid, gluconic acid, o-, m-, p-phthalic acid, tetrahydrophthalic acid , Hexahydrophthalic acid and the like.

As the glycol, for example, alkanediol, oxaalkanediol, diol obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to bisphenol A type, and the like are used. In addition, a monohydric or trihydric alcohol can be used. Examples of alkanediols include, for example, ethylene glycol, 1,2-propylene glycol,
Examples include 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6 hexanediol, and cyclohexanediol. Examples of the oxaalkanediol include diethylene glycol and triethylene glycol. Examples of the monohydric or trihydric alcohol used in combination with these glycols include octyl alcohol, oleyl alcohol, and trimethylolpropane. The synthesis of unsaturated polyester is generally carried out under heating, and the reaction proceeds while removing by-produced water. At this time, in order to prevent thermal polymerization, it is preferable to use a polymerization inhibitor. Generally, those having high heat resistance are required for laminate applications, but when producing unsaturated polyester, select a raw material that increases the crosslink density and reactivity, or use hydrogenated bisphenol A type as a raw material. By using a glycol having a rigid structure, an unsaturated polyester having a high glass transition temperature and thus having high heat resistance can be obtained.

The radical polymerizable resin (a) used in the present invention is usually 15 to 80 parts by weight, preferably 2 to 100 parts by weight in total of the resin compositions (a), (b) and (c).
It is preferred to use from 0 to 70 parts by weight. The above vinyl esters and unsaturated polyesters can be used alone or in combination. The radical polymerizable monomer (b) used in the present invention is a polymerizable monomer having at least one double bond in the molecule, and is used as a reactive diluent for ensuring the fluidity of the compound during molding. You. Examples of the radical polymerizable monomer (b) include:
Unsaturated fatty acids such as acrylic acid and methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2 -Unsaturated carboxylic acid esters such as ethylhexyl acrylate and dodecyl acrylate, unsaturated nitrogen monomers such as (meth) acrylamide and (meth) acrylonitrile, styrene, vinyltoluene, divinylbenzene, pt-butylstyrene and the like. Aromatic vinyl compound, ethylene glycol di (meth) acrylate,
Diethylene glycol di (meth) acrylate, 1,4
Examples include polyfunctional (meth) acrylates such as butanediol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. These can be used alone or in combination. Of these, styrene is particularly preferably used.

[0010] The amount of the radical polymerizable monomer (b) used is usually 10% in total of the resin compositions (a), (b) and (c).
The range of 5 to 80 parts by weight of 0 parts by weight is preferred. However, in order to make the cured product exhibit higher heat resistance,
It is preferable not to increase the amount of the radical polymerizable monomer (b) so much, and it is preferable that the amount is in the range of 5 to 60 parts by weight. The polymer fine particles (c) having a hydroxyl group used in the present invention are not particularly limited, and those having various structures such as a multilayer structure having two or more layers, a salami structure, and the like can be used. Although the particle size varies depending on the preparation method, it is usually about 0.05 μm to 100 μm. Polymer fine particles having a multilayer structure can be easily synthesized by, for example, seed emulsion polymerization or multi-stage suspension polymerization. In the present invention, acrylic polymer fine particles having a multilayer structure synthesized by seed emulsion polymerization are particularly preferably used.

A single-layer structure can be synthesized by a general-purpose manufacturing method. The case of multilayer acrylic fine particles synthesized by seed emulsion polymerization or multistage suspension polymerization, which is a more preferred embodiment, will be described below. Each layer of the multilayer acrylic fine particles is synthesized by homopolymerizing or copolymerizing a radical polymerizable monomer. Examples of the monomer used herein include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexy (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl (meth) acrylate. Examples thereof include (meth) acrylates, nitrile-containing monomers such as (meth) acrylonitrile, aromatic vinyls such as styrene, vinyltoluene and α-methylstyrene, and dienes such as butadiene and isoprene. In addition, monomers having a functional group other than hydroxyl group, such as acid-containing monomers such as (meth) acrylic acid and itaconic acid, epoxy-group-containing monomers such as glycidyl (meth) acrylate, and amino-group-containing monomers such as diaminoethyl (meth) acrylate Can also be copolymerized. In order to control the swellability of the polymer particles in the resin composition, ethylene glycol di (meth) acrylate, butanediol di (meth)
It is preferable to form a crosslinked polymer by copolymerizing a multifunctional monomer such as acrylate, divinylbenzene, allyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. The amount of the polyfunctional monomer to be used is generally 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, based on 100 parts by weight of each layer.

In the multilayer polymer fine particles, it is necessary that at least one of the layers has a hydroxyl group, but it is preferable that the outermost layer has a hydroxyl group. The method of introducing a hydroxyl group into the outermost layer and other layers is not particularly limited, but a method of copolymerizing a hydroxyl group-containing monomer is simple. The hydroxyl group-containing monomer used here includes hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth)
Acrylate and the like. The amount of these used is such that the hydroxyl equivalent of the hydroxyl group-containing layer in the polymer fine particles is 0.1 to 3;
00 mgKOH / g, preferably 0.5 to 200 mgK
OH / g, more preferably 1.0 to 100 mgKOH /
g. If the hydroxyl group equivalent in the hydroxyl group-containing layer is less than 0.1 mgKOH / g, the effect of improving the low coefficient of thermal expansion and drilling properties may not be sufficiently obtained. Conversely, if it exceeds 300 mgKOH / g, the dispersibility in the resin may be insufficient. May decrease. The hydroxyl equivalent in the polymer fine particles is usually 0.01 to 50 mgKOH /
g, preferably 0.05 to 40 mg KOH / g, more preferably 0.1 to 30 mg KOH / g. The outermost layer of the multilayer polymer fine particles (c)
It is preferable to be composed of a glassy polymer from the viewpoint of dispersibility in resin and easy handling of particles. The glassy polymer referred to here has a glass transition temperature (Tg) of room temperature (2 g).
5 ° C.) or higher, preferably 50 ° C. or higher, more preferably 7 ° C.
A polymer at 0 ° C or higher. Tg is the DS of the particle
C measurement is performed, and the peak temperature is easily obtained.
The Tg of the polymer can be easily adjusted by changing the monomer composition at the time of synthesis.

The thickness of the outermost layer in the multilayer polymer fine particles is usually 1 to 30% with respect to the radius of the polymer fine particles.
Preferably it is 2 to 20%, more preferably 3 to 15%. It is advantageous that at least one of the layers excluding the outermost layer is made of a rubbery polymer from the viewpoint of imparting toughness to the cured resin and further improving workability. The Tg of the rubbery polymer is 20 ° C. or less, preferably 10 ° C.
Or less, more preferably 0 ° C. or less. Examples of such multi-layer polymer fine particles include a so-called core-shell polymer having a rubbery polymer / glassy polymer configuration. Further, those having a three-layer structure such as a glassy polymer / rubber-like polymer / glass-like polymer and those having a multilayer structure more than that can be used. The particle size of the multilayer polymer fine particles is usually 0.05 to 2 μm when synthesized using seed emulsion polymerization, and is usually 1 to 100 μm when synthesized using multi-stage suspension polymerization. . In a laminate prepared using the resin composition of the present invention, transparency may be required. In such a case, by setting the refractive index of the polymer fine particles close to the refractive index of the cured product of the matrix resin, a transparent cured product can be obtained. Specifically, the object is achieved by setting the difference in refractive index between the cured matrix resin and the polymer fine particles to 0.05 or less, preferably 0.03 or less, and more preferably 0.02 or less. When the polymer fine particles of the present invention are synthesized by seed emulsion polymerization or multistage suspension polymerization, the refractive index of the matrix resin can be easily brought close to the matrix resin by adjusting the monomer composition at the time of synthesis. The glass transition temperature of the cured product of the resin composition comprising the radically polymerizable resin (a), the radically polymerizable monomer (b) and the polymer fine particles having a hydroxyl group (c) is preferably 120 ° C. or higher, and 130 ° C. or higher. Is more preferable. The application of the resin composition of the present invention is a laminated board, and in this application, high heat resistance is required. Therefore, the cured product of the resin must be glassy up to around this temperature and have a sufficient elastic modulus. Is preferred. The laminate is required to have good drill workability. To this end, a cured product of the resin composition comprising (a), (b) and (c) has a fracture toughness of a certain level or more. It must have a value. The specific fracture toughness value of the cured product is usually 0.7 MNm ^3/2 or more, preferably 1.
0 MNm ^3/2 or more, more preferably 1.2 MNm
^3/2 or more.

The resin composition of the present invention can use a flame retardant, a fiber reinforcing material, and an inorganic filler (d) as a thickener. As the flame retardant, for example, aluminum hydroxide,
Glass powder, calcium carbonate, talc, silica, clay, glass balloon and the like can be used, and among them, aluminum hydroxide can be preferably used. Glass fiber, carbon fiber, glass cloth, glass mat, glass paper, etc. can be used as the fiber reinforcing material of the laminate. Examples of the thickener include oxides and hydroxides of magnesium and calcium. The amount of the inorganic filler is usually 5 to 400 parts by weight based on 100 parts by weight of the resin composition comprising (a), (b) and (c). To the composition of the present invention, a rubber component can be added for improving physical properties as a cured product such as toughness and impact resistance. The rubber component to be added includes carboxyl group terminal NBR, epoxy group terminal NBR, vinyl group terminal NB
Liquid rubbers such as R and modified products thereof.
The amount of the rubber component used is based on 100 parts by weight of the resin composition.
Usually, it is 0.5 to 30 parts by weight.

In the composition of the present invention, if necessary, other additives conventionally used, such as a low-shrinkage agent and an internal mold release agent, can be used. As a low contraction agent,
Saturated polyester, polymethyl methacrylate, polyvinyl acetate, cross-linked polystyrene, styrene butadiene (block) copolymer and its hydrogenated product, vinyl acetate-styrene (block) copolymer, (meth) acryl-styrene (block) copolymer Coalescence or the like is used. Examples of the internal release agent include metal soaps typified by calcium stearate and zinc stearate, silicon and fluorine-based organic compounds, and phosphoric acid-based compounds. The resin composition of the present invention can be easily cured by adding a curing agent used for curing a usual radically polymerizable resin and, if necessary, a curing accelerator. Examples of the curing agent used in the present invention include organic peroxides such as methyl ethyl ketone peroxide, t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide and cumene hydroperoxide. The amount of the curing agent used is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin composition.
More preferably, it is 0.5 to 3 parts by weight. Examples of the curing accelerator include cobalt naphthenate, cobalt octoate, dimethylaniline, acetylacetone and the like. The amount of the curing accelerator used is preferably 0.01 to 3 parts by weight based on 100 parts by weight of the resin composition. As the substrate to be impregnated with the resin composition of the present invention, any of those conventionally used for laminated boards, such as glass nonwoven fabric, glass woven fabric, and paper substrate, can be used. The method of impregnating the base material with the resin structure is not particularly limited, and any method known per se is used. The glass fiber woven fabric impregnated with the resin composition of the present invention is used as a surface layer, and a composite laminate obtained by laminating a glass fiber nonwoven fabric impregnated with the resin composition of the present invention as an inner layer is compressed and cured, whereby the present invention is applied. A composite laminate is obtained. This laminate is heat resistant, water resistant,
It has excellent drill workability and low thermal expansion in addition to toughness, and is particularly useful as a printed wiring board and the like.

[0016]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Production Examples, Examples, Comparative Examples, and Test Examples, but the present invention is not limited thereto. Note that “parts” in Production Examples, Examples, Comparative Examples, and Test Examples all represent parts by weight. Abbreviations used in Production Examples, Examples, and Comparative Examples are as follows. Monomer n-butyl acrylate BA 2-ethylhexyl acrylate 2EHA methyl methacrylate MMA ethyl acrylate EA styrene St 1,4-butylene glycol diacrylate BGA divinylbenzene DVB allyl methacrylate AIMA 2-hydroxylethyl methacrylate HEMA surfactant sodium dioctyl sulfosuccinate SSS Others Deionized water DIW Sodium bicarbonate SBC Sodium persulfate SPS Measurement method of particle diameter: Measured by dynamic light scattering method using a dynamic light scattering measurement device (LPA-3000 / LPA-3100) manufactured by Otsuka Electronics Co., Ltd. .

Production Example 1 Production of Multilayer Polymer Fine Particles (1) In a 2 liter polymerization vessel equipped with a reflux condenser, 506 g of DIW was added.
2.5 g of 1% SSS aqueous solution, 16.4% 1% SBC aqueous solution
g, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream. After the temperature was raised, 8 g of EA was added, and after stirring for 10 minutes, 2%
A seed latex was obtained by adding 4.1 g of the SPS aqueous solution and further stirring for 1 hour. Continue at 70 ° C
After adding 51 g of 2% SPS aqueous solution in
631 g, BGA 13.4 g, AIMA 26.9 g, 1
The monomer emulsion for forming the first layer consisting of 408 g of a 1% aqueous SSS solution and 68 g of a 1% aqueous SBC solution was continuously fed over 240 minutes. After the feed was completed, the mixture was further stirred at 70 ° C. for 60 minutes to perform an aging reaction. Next, 70 ° C
After adding 7.2 g of a 2% SPS aqueous solution while maintaining the temperature, 114.8 g of MMA, 4 g of HEMA, 1.2 g of BGA
g, 1% SSS aqueous solution 48g, 1% SBC aqueous solution 12g
Was fed continuously over 150 minutes. After the feed was completed, the temperature was raised to 80 ° C., and the mixture was further stirred for 60 minutes to perform an aging reaction. After completion of the aging reaction, the mixture was cooled to 30 ° C., filtered through a 300 mesh stainless steel wire gauze, and the hydroxyl equivalent of the second layer was 14.4.
mgKOH / g (2.2 mgKOH for the whole particles)
/ G), a latex of multilayer polymer fine particles (1) having a weight average particle diameter of 0.53 μm was obtained. This latex was once frozen at −30 ° C., thawed, dehydrated and washed with a centrifugal dehydrator, and further dried at 60 ° C. for 24 hours to obtain multilayer polymer fine particles (1).

Production Example 2 Production of Multilayer Polymer Fine Particles (2) In a 2-liter polymerization vessel equipped with a reflux condenser, 506 g of DIW was added.
42 g of a 1% SSS aqueous solution and 28 g of a 1% SBC aqueous solution were charged and heated to 70 ° C. while stirring under a nitrogen stream. After the temperature was raised, 14 g of St was added. After stirring for 10 minutes, 2% SP was added.
28 g of an aqueous S solution was added, and the mixture was further stirred for 1 hour to obtain a seed latex. Subsequently, at 70 ° C., 38.4 g of a 2% aqueous SPS solution was added, and then 2EH
A 375.7 g, St 246 g, DVB 1.3 g, AIM
A3.1 g, 0.5% SSS aqueous solution 640 g, 1% SB
The monomer emulsion for forming the first layer consisting of 64 g of the C aqueous solution was continuously fed over 240 minutes. After the feed was completed, the mixture was further stirred at 70 ° C. for 60 minutes to perform an aging reaction. Next, while maintaining at 70 ° C., 9.6 g of a 2% SPS aqueous solution was added, and then 128 g of MMA, 16 g of St,
EMA 8g, BGA 8g, 1% SSS aqueous solution 64g, 1
The monomer emulsion for forming the second layer consisting of 16 g of the aqueous SBC solution was continuously fed over 150 minutes. After the feed was completed, the temperature was raised to 80 ° C., and the mixture was further stirred for 60 minutes.
An aging reaction was performed. After completion of the aging reaction, the mixture was cooled to 30 ° C., filtered through a 300-mesh stainless steel wire gauze, and the hydroxyl equivalent of the second layer was 21.6 mgKOH / g (4.3 mgKOH / g with respect to the whole particles), and the weight average particle diameter 0.2
A latex of multilayer polymer fine particles (2) having a thickness of 0 μm was obtained. This latex was once frozen at −30 ° C., thawed, dehydrated and washed with a centrifugal dehydrator, and further dried by blowing air at 60 ° C. all day and night to obtain multilayer polymer fine particles (2).

Production Example 3 Synthesis of Vinyl Ester Resin (1) In a four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introducing device and a thermometer, an epototo YDB400 (brominated bisphenol A type epoxy resin manufactured by Toto Kasei Co., Ltd.) , 800 g of epoxy equivalent, 400 g / eq), 172 g of methacrylic acid, 0.2 g of triphenylphosphine and 0.1 g of hydroquinone were reacted at 120 ° C. for 8 hours to obtain 972 g of a vinyl ester having an acid value of 1.8.
Then, the vinyl ester was converted into styrene monomer (648 g).
Then, the desired vinyl ester resin (1) was obtained. Example 1 Vinyl ester resin (1) obtained by the above resin synthesis example, Polymer 9802, an unsaturated polyester resin containing maleic acid as an acid component, propylene glycol as a glycol component, and diluted with styrene (Takeda Pharmaceutical Co., Ltd.) After mixing the styrene monomer in the composition shown in [Table 1], the multi-layered polymer fine particles (1) were added in the same manner as shown in [Table 1] while heating and stirring at 60 ° C., and the mixture was mixed for 1 hour. A dispersed radically polymerizable resin composition (A) was obtained. Example 2 The vinyl ester resin (1) obtained by the above resin synthesis example, Polymer 5602 (Takeda Pharmaceutical Co., Ltd.) which is an unsaturated polyester resin diluted with styrene using maleic acid as an acid component and propylene glycol as a glycol component After mixing styrene monomer in the composition shown in [Table 1], multi-layer polymer fine particles (2) were added in the same manner as shown in [Table 1] while heating and stirring at 60 ° C., and the mixture was mixed for 1 hour. A dispersed radical polymerizable resin composition (B) was obtained.

Comparative Example 1 The vinyl ester resin (1) obtained by the above-mentioned resin synthesis example, and a polymer 56 which is an unsaturated polyester resin
02 (manufactured by Takeda Pharmaceutical Co., Ltd.) and a styrene monomer in a mixing ratio as shown in Table 1, and then heated to 60 ° C. and stirred to obtain staphyloid AC3355, which is an acrylic polymer fine particle having no hydroxyl group (weight average particle). Diameter 0.50
μm; manufactured by Takeda Pharmaceutical Co., Ltd.) in the same manner as in Table 1 to obtain a radical polymerizable resin composition (C) in which polymer fine particles are dispersed over 1 hour. Comparative Example 2 Vinyl ester resin (1) obtained by the above-mentioned resin synthesis example, and polymer 98 which is an unsaturated polyester resin
02 (manufactured by Takeda Pharmaceutical Co., Ltd.), a styrene monomer was mixed in the proportions shown in Table 1, and then heated to 60 ° C. and stirred to form nitrile-based rubber-based fine particles having no hydroxyl group.
80 g of TBN (manufactured by BF Goodrich Co., Ltd.) was added, and a radically polymerizable resin composition (D) was obtained over 1 hour.

Test Example 1 Preparation of Cured Product of Resin Composition Each of radical polymerizable resin compositions (A) to (D) was prepared as follows.
To 100 parts by weight, 1 part by weight of a polymerization initiator ("Perbutyl O" manufactured by NOF Corporation) was added, and the mixture was heated at 100 ° C for 30 minutes and then at 175 ° C for 30 minutes to obtain a cured product. The physical properties of were measured and are shown in Table 1. Preparation of Laminate A 0.18 m thick glass fiber woven fabric manufactured by Nitto Boseki Co., Ltd.
m, a glass fiber woven cloth “WEA7628” was used. As a thermosetting resin composition (compound) to be impregnated into the glass fiber woven fabric, 1 part by weight of a polymerization initiator ("Perbutyl O" manufactured by NOF Corporation) was added to 100 parts by weight of each of the radically polymerizable resin compositions. Aluminum hydroxide as inorganic filler (CL-3 manufactured by Sumitomo Chemical Co., Ltd.)
10 ") 30 parts by weight were used. Glass fiber non-woven fabric is manufactured by Japan Vilene Co., Ltd. (basis weight 45 g /
m ² ) was used. As a thermosetting resin composition (compound) to be impregnated into a glass fiber nonwoven fabric, 100 polymer parts of each of the above radical polymerizable resin compositions was used, and as an inorganic filler, aluminum hydroxide ("CL" manufactured by Sumitomo Chemical Co., Ltd.)
-310 ") 150 parts by weight.
Next, two glass fiber non-woven fabrics impregnated with the compound were placed at the center, and one glass fiber woven fabric impregnated with the compound was disposed above and below the two glass fiber non-woven fabrics, thereby producing a composite laminate. 18 μm thick copper foil (300 mm ×
300 mm). Next, this laminate was sandwiched between metal plates, and was heated and cured at 110 ° C. for 60 minutes in a flat state, and further after-cured at 170 ° C. for 30 minutes.
A 1.6 mm double-sided copper-clad composite laminate was obtained. In addition, the continuous flow direction of the glass fiber woven fabric, the glass fiber nonwoven fabric, and the copper foil was set to the vertical direction, and when laminating, the materials were stacked so that the vertical direction of each material was the same. Various physical properties of the obtained copper-clad laminate were measured and are shown in [Table 1].

[0022]

[Table 1] Method for measuring fracture toughness value of cured product of resin composition: ASTM
Measurement method of heat resistance (Tg) according to D 5045: The dynamic viscoelasticity of a cured product of the resin composition was measured, and the temperature at which tan δ had a peak value was defined as Tg, and this Tg was used as an index of heat resistance. Measuring method of alkali resistance: After removing the copper foil from the copper-clad laminate, immersed in a 10% aqueous NaOH solution at 80 ° C. for 1 hour and measured the weight loss value. Measuring method of linear expansion coefficient: An average linear expansion coefficient in a temperature range of 40 to 100 ° C. was obtained from a laminate obtained by removing a copper foil by etching from a copper-clad laminate according to JIS K7179. Measuring device: Rigaku Corporation TMA device (TAS-1)
00) Measurement conditions: heating rate 5 ° C./min, measurement temperature range 40 to
150 ° C., load 1 g Evaluation of drill workability: Three copper-clad laminates cut to 250 mm × 250 mm were stacked, drill diameter 0.9 mmφ, drill rotation number 6000 rpm, feed rate 50 μm / r.
Drilling was performed up to 4500 hits under the conditions of ev, and then the side surface of the hole, the surface of the substrate, and the back surface were observed with a microscope. The results were evaluated from the results of microscopic observation, and the results are shown in Table 1 where ◎ indicates a very good result, を indicates no practical problem, and △ indicates a practical level.

[0023]

According to the present invention, it is possible to simultaneously solve the two problems of good drill workability and a low coefficient of linear expansion in a metal foil-clad laminate which could not be satisfied by the prior art.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 290/06 B29C 67/14 X (72) Inventor Hiroshi Takeuchi 2-chome, Jusanhoncho, Yodogawa-ku, Osaka-shi, Osaka No. 17-85 Takeda Pharmaceutical Co., Ltd. Chemical Company (72) Inventor Koji Shibata 2-17-13 Honhoncho, Yodogawa-ku, Osaka-shi, Osaka 17-85 Takeda Pharmaceutical Co., Ltd. Chemical Company (72) Invention Person Isao Hirata 1048 Kadoma Kadoma, Kadoma-shi, Osaka Matsushita Electric Works, Ltd. (72) Inventor Shigehiro Okada 1048 Kadoma Kadoma, Kadoma-shi, Osaka Matsushita Electric Works F-term (reference) 4F072 AB28 AB29 AD08 AD38 AG03 AH25 AL09 AL13 4F205 AA41 AA43 AB11 AB19 AD04 AD14 AH36 HA14 HA25 HA33 HA45 HB01 HC06 HC16 HK03 HK04 HK27 4J011 PA07 PA13 PA15 PA69 PB08 PB22 PC02 4J027 AB02 AB 06 AB07 AB08 AB15 AB16 AB17 AB18 AE02 AE03 AE04 AF05 BA04 BA05 BA06 BA07 BA08 BA09 BA10 BA14 BA20 BA26 BA27 CA03 CA14 CA18 CA19 CC02

Claims (10)

[Claims] 1. A laminate resin composition comprising a radically polymerizable resin (a), a radically polymerizable monomer (b) and polymer fine particles (c) having a hydroxyl group. 2. The resin composition for a laminate according to claim 1, wherein the polymer fine particles (c) having a hydroxyl group are multilayer polymer fine particles. 3. The resin composition for a laminate according to claim 1, wherein the polymer fine particles (c) having a hydroxyl group are polymer fine particles having a multilayer structure having a hydroxyl group in the outermost layer. 4. The resin composition for a laminate according to claim 2, wherein the thickness of the outermost layer of the polymer fine particles (c) having a hydroxyl group is 1 to 30% with respect to the particle radius. 5. The hydroxyl group-containing layer of the polymer fine particles (c) having a hydroxyl group has an equivalent of 0.1 to 300 m in the hydroxyl group.
The resin composition for a laminate according to any one of claims 1 to 4, wherein the resin composition is gKOH / g. 6. The resin composition for a laminate according to claim 1, further comprising an inorganic filler (d). 7. The compounding ratio of the inorganic filler (d) is (a),
The resin composition for a laminated board according to claim 6, wherein the amount is 5 to 250 parts by weight based on 100 parts by weight of the resin composed of (b) and (c). 8. The cured product of the resin composition comprising (a), (b) and (c) has a glass transition temperature of 120 ° C. or more and a fracture toughness of 0.7 MNm ^3/2 or more. Item 6. The resin composition for a laminate according to any one of Items 1 to 5. 9. A laminate obtained by curing a substrate impregnated with the resin composition for laminate according to any one of claims 1 to 8. 10. A glass fiber woven fabric impregnated with the resin composition according to any one of claims 1 to 8 as a surface layer.
A composite laminate laminated and cured by using, as an inner layer, a glass fiber nonwoven fabric impregnated with the resin composition according to any one of items 8 to 8.