JPH0582290B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an electrical laminate using an unsaturated polyester resin composition with improved impact resistance. The term "electrical laminate" as used herein means, for example, a laminate or a metal foil-covered laminate used as a substrate for various electronic components, and the shape of the electrical laminate is a plate with a thickness of 0.5 to 5 mm. Unsaturated polyester resin is a typical thermosetting resin that is used in a wide range of fields due to its good physical properties and moldability, but its application field is limited due to its insufficient impact resistance. Restricted. Generally, in order to improve the impact resistance of unsaturated polyester resin, it is carried out to modify it using an acid or alcohol with a long alkyl chain as a component, but this method does not improve the impact resistance. However, rigidity such as flexural modulus is significantly impaired. Similarly, polybutadiene rubber has been added as a component to improve impact resistance, but with this method, the premix quickly separates into two layers, upper and lower, due to poor compatibility. Otherwise, the viscosity increases and impregnating properties and other molding workability are significantly impaired. Various other methods have been proposed for the purpose of improving impact resistance, but even if they can improve impact resistance, they significantly lose some of the excellent performance originally possessed by unsaturated polyester resins. This results in damage and is of little practical value. As a result of extensive research aimed at improving the impact resistance of unsaturated polyester resins without sacrificing their inherent excellent properties, the present inventors discovered a specific compound as a component of the crosslinking monomer. The present invention was achieved by discovering that by using a flexible monomer, impact resistance can be highly improved without impairing molding workability such as impregnability or rigidity such as flexural modulus. That is, the present invention provides unsaturated alkyds (A) from 90 to 20
Parts by weight and general formula of 0.1 to 50% by weight of the total amount of crosslinking monomers

[Formula, R ₁ is hydrogen or methyl group, R ₂ is C ₂ ~ ₁₀
divalent aliphatic hydrocarbon group, R ₃ is hydrogen or C ₁ to ₁₀
a hydrocarbon group, n means a positive integer of 1 to 20. ) Crosslinking monomer (B) containing a flexible monomer 10~
80 parts by weight of an electrical laminate using an unsaturated polyester resin composition. In the present invention, the unsaturated alkyd (A) is an unsaturated dicarboxylic acid, a mixture of an unsaturated dicarboxylic acid and an unsaturated monocarboxylic acid or a saturated dicarboxylic acid, and a polyhydric alcohol, or a polyhydric alcohol and a monoalcohol. It is obtained by dehydration condensation from a mixture. As an unsaturated dicarboxylic acid,
Examples include maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, and anhydrides thereof. Examples of unsaturated monocarboxylic acids include maleated dicyclopentadiene and 10-undecenoic acid. Examples of the saturated dicarboxylic acid include adipic acid, succinic acid, phthalic acid, isophthalic acid, terephthalic acid, and anhydrides thereof. Further, halogen-substituted derivatives thereof, such as chlorendic acid, tetrabromophthalic acid, tetrabromoterephthalic acid, and anhydrides thereof, may also be mentioned. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol,
Examples include hexanediol, neopentyl glycol, hydrogenated bisphenol A, adducts of bisphenol A with ethylene oxide and propylene oxide, epoxidized bisphenol, glycerin, and pentaerythritol. Examples of monoalcohols include hydroxylated dicyclopentadiene, cinnamyl alcohol, and the like. Further, halogen-substituted derivatives thereof, such as dibromoneopentyl glycol and tetrabromobisphenol A adducts with ethylene oxide and propylene oxide, are also included. In addition, post-halogenated unsaturated alkyds, such as those obtained by partially using maleated dicyclopentadiene or tetrahydrophthalic anhydride as the acid component, and hydroxylated dicyclopentadiene or cinnamyl alcohol as the alcohol component, can also be used. Examples include chemical compounds. In particular, from the viewpoint of heat softening resistance, molding workability, impact resistance, and flame retardancy, bromine obtained by reacting an unsaturated alkyd or maleated cydiclopentadiene with a polyhydric carboxylic acid and a polyhydric alcohol, and then brominating the reaction. Preferably, it is a mixture of a containing unsaturated alkyd and a soft unsaturated alkyd for adjusting hardness. The amount of unsaturated alkyd to be used varies depending on the purpose and use, but is preferably 90 to 20 parts by weight, especially 80 parts by weight.
~50 parts by weight is preferred. If it exceeds 90 parts by weight, the viscosity of the composition will be too high and workability will tend to deteriorate, and if it is less than 20 parts by weight, curability will decrease and impact resistance will also decrease. The flexible monomer which is an essential component of the crosslinking monomer (B) in the present invention is represented by the following general formula.

[Formula, R ₁ is hydrogen or methyl group, R ₂ is C ₂ ~ ₁₀
divalent aliphatic hydrocarbon group, R ₃ is hydrogen or C ₁ to ₁₀
a hydrocarbon group, n means a positive integer of 1 to 20. ) Such flexible monomers are typically obtained by reacting acrylic acid or methacrylic acid with ethylene oxide, propylene oxide, or tetrahydrofuran, followed by an addition reaction with ε-caprolactone. Specific examples include ε-caprolactone adducts of hydroxyethyl (meth)acrylate, ε-caprolactone adducts of hydroxypropyl (meth)acrylate, and ε-caprolactone adducts of hydroxybutyl (meth)acrylate. Particularly preferred is an adduct of hydroxyethyl methacrylate with ε-caprolactone (8 mol). The amount of the flexible monomer used in the crosslinking monomer (B) is preferably 0.1 to 50% by weight based on the total amount of (B). If it is less than 0.1%, the effect of improving impact resistance is small, and if it exceeds 50% by weight, the viscosity tends to increase and the rigidity tends to decrease significantly. In particular, it is preferably 5 to 30% by weight based on the total amount of crosslinking monomers. Other crosslinking monomers (B) are not limited as long as they are used for ordinary unsaturated polyester resins, and styrene is a typical example, but α-methylstyrene, vinyltoluene, chlorostyrene, divinyl Aromatic vinyl monomers such as benzel,
Ethyl acrylate, butyl acrylate, 2-
Examples include acrylic esters such as ethylhexyl acrylate and hydroxyethyl acrylate, methacrylic esters such as methyl methacrylate and hydroxy-ethyl methacrylate, and allyl compounds such as diallyl phthalate and triallyl cyanurate. The resin composition of the present invention can be cured using a general-purpose organic peroxide. In particular, the use of one or more peroxides selected from peroxyketals, dialkyl peroxides, and peroxyesters improves the soldering heat resistance of the laminate.
It gives particularly favorable results in terms of electrical insulation properties and adhesion. Examples of preferred organic peroxides include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, etc. as paoxyketals. , di-t-butyl peroxide as dialkyl peroxides, and t-butyl peroxybenzoate as peroxy esters. These are 0.5 to resin composition
Use around 2.0 parts. Note that the curing catalyst is not limited to these, and known curing catalysts such as a curing catalyst that is sensitive to light or a curing catalyst that is sensitive to radiation and electron beams can also be used together with an organic peroxide or alone. Furthermore, the resin composition of the present invention can contain an additive type plasticizer and a flame retardant. Examples of the plasticizer include commercially available ester plasticizers, tung oil, soybean oil, linseed oil, and derivatives thereof. Flame retardants include trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, triphenyl phosphite, and tris(chlorethyl).
Phosphorous flame retardants such as phosphates, halogen flame retardants such as chlorinated paraffin, tetrabromobisphenol A, and tetrabromodiphenyl ether, antimony compounds such as antimony trioxide and sodium antimonate, zinc borate, aluminum hydroxide, etc. can be mentioned. Further, if necessary, various additives such as other polymers or fillers, acid value inhibitors, lubricants, and inorganic pigments can be included. The unsaturated polyester resin composition of the present invention can be used in the production of electrical laminates according to known methods. That is, a base material is impregnated with a resin composition, a plurality of impregnated base materials are laminated, and in the case of a metal foil-clad laminate, metal foil is layered on one or both sides,
An electrical laminate can be obtained by hardening and molding. The base material can be a glass base material such as glass cloth or glass matte, preferably a cellulose base material or a mixed base material thereof, and particularly preferably, for example, kraft paper or linter paper can be used. For example, JP-A-56-
It is preferable to pre-impregnate the substrate with the unsaturated polyester resin composition as described in No. 98136 before impregnating the substrate. Furthermore, when laminating and curing the resin-impregnated base materials mentioned above, it is best to continuously cure the resin-impregnated base materials under virtually no pressure conditions, as disclosed in JP-A-56-98136. This is a good method. The resin composition of the present invention has good impregnation properties into substrates, and the obtained laminate has excellent impact resistance, as well as good rigidity and heat softening resistance. The present invention will be explained in detail below with reference to Examples. In the examples, "parts" and "%" are based on weight. Example 264 g of dicyclopentadiene, maleic anhydride
Put 196 g and 38 g of water into a flask equipped with a stirrer, thermometer, and reflux device, and heat to 120 to 140 g under nitrogen flow.
The reaction was carried out at ℃ for 3 hours to quantitatively obtain maleated dicyclopentadiene with an acid value of 226. This was reacted with 98 g of maleic anhydride, 94 g of ethylene glycol, and 111 g of diethylene glycol using xylene as an azeotropic solvent at 150 to 210° C. for 8 hours to obtain an unsaturated alkyd with an acid value of 19. Into two flasks equipped with a stirrer, a thermometer, and a dropping funnel with a side pipe, 767 g of methylene chloride was charged with the unsaturated alkyd, dissolved with stirring, cooled to below 20°C with ice water, and added with bromine under a nitrogen stream.
288g was added dropwise over 1.5 hours. After methylene chloride was distilled off, 395 g of styrene to which 0.28 g of hydroxone had been added was added to obtain a brominated unsaturated polyester with a styrene concentration of 28%. 47.5 parts of this brominated unsaturated polyester, 33 parts of soft unsaturated polyester (Polymer 6320F, styrene content 37%, manufactured by Takeda Pharmaceutical Company Limited), 10 parts of aluminum hydroxide, 3.5 parts of antimony trioxide, organic peroxide curing 1 part of a catalyst (Perhexa 3M, manufactured by NOF Corporation) and 5 parts of ε-caprolactone (8 mol) adduct of hydroxyethyl methacrylate were thoroughly kneaded with a roll to obtain a flame-retardant unsaturated polyester resin composition. This resin composition was impregnated into a methylolmelamine-treated paper base material, five impregnated base materials were laminated, and the resin composition was heated to 160 °C for 15 minutes at 100°C.
A laminate with a thickness of 1.55 mm was obtained by heating and curing at ℃ for 10 minutes. Table 1 shows the properties of the flame-retardant unsaturated polyester resin composition and the physical properties of the laminate. Comparative Example A flame-retardant unsaturated polyester resin composition and a laminate were obtained by the same procedure as in the above example except that 5 parts of styrene was used instead of 5 parts of ε-caprolactone (8 mol) adduct of hydroxyethyl methacrylate. Ta. Table 1 shows the properties of the flame-retardant unsaturated polyester resin composition and the physical properties of the laminate.

[Table] From Table 1, the composition and laminate of the present invention are as follows:
It can be seen that the impact strength is significantly improved, and there is almost no increase in viscosity or decrease in rigidity.

Claims (1)

[Claims] 1 90 to 20 parts by weight of an unsaturated alkyd (A) and 0.1 to 50% by weight of the total amount of crosslinking monomers of the general formula [formula] (wherein R ₁ is hydrogen or a methyl group, _R2 is _C2 ~ ₁₀
divalent aliphatic hydrocarbon group, R ₃ is hydrogen or C ₁ to ₁₀
a hydrocarbon group, n means a positive integer of 1 to 20. ) Crosslinking monomer (B) 10 containing a flexible monomer
An electrical laminate made by laminating and curing a plurality of base materials impregnated with an unsaturated polyester resin composition comprising ~80 parts by weight. 2. The unsaturated alkyd is a mixture of a bromine-containing unsaturated alkyd obtained by reacting maleated dicyclopentadiene, a polycarboxylic acid, and a polyhydric alcohol, and then brominating the mixture, and an unsaturated alkyd for hardness adjustment. The electrical laminate according to item 1.