JPS606715A - Unsaturated polyester resin composition and laminated sheet - Google Patents

Abstract

PURPOSE:The titled composition of excellent impact resistance, comprising an unsaturated alkyd and a crosslinking monomer containing a specified flexible monomer. CONSTITUTION:An unsaturated alkyd is obtained by mixing a bromine-containing unsaturated alkyd obtained by reacting maleinized dicyclopentadiene with a polycarboxylic acid and a polyalcohol and brominating the product with a flexible alkyd for hardness control. 90-20pst.wt. above unsaturated alkyd is mixed with 10-80pts.wt. crosslinking monomer (e.g., styrene) containing 0.1-50wt% flexible monomer of the formula (wherein R1 is H or methyl, R2 is a 2-10C bivalent aliphatic hydrocarbon group, R3 is H or a 1-10C hydrocarbon group, and n is 1-20) to obtain an unsaturated polyester resin composition. A plurality of bases impregnated with the resin composition are laminated and cured by heating to obtain a laminated sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an unsaturated polyester resin composition with improved impact resistance and an electrical laminate using the resin composition. The term "electrical laminate" as used herein refers to a laminate or a metal foil-covered laminate that is used, for example, as a substrate for various electronic components, and refers to a plate-like product having a thickness of 0.5 to 5 mm.

Unsaturated polyether 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 fields are limited due to its insufficient impact resistance. is recieving.

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, for the purpose of improving impact resistance, polybutadiene rubber is also added as a component, but with this method, due to poor compatibility, the premix becomes the upper 12 layers in a short period of time. Separation (-) or thickening will significantly impair molding workability such as impregnation. Various other methods have been proposed for the purpose of improving impact resistance, but none of them improve impact resistance. Even if it could be improved, it would result in a significant loss of some of the excellent performance that unsaturated polyester resins have traditionally had, and would have 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 (wherein R1 is hydrogen or a methyl group, R2 is a divalent aliphatic hydrocarbon group of 02 to 10, R3 is hydrogen or a hydrocarbon group of 01 to IO, and n is a positive integer of 1 to 20.) monomer (B) 10-8
0 parts by weight of an unsaturated polyester resin composition, and an electrical laminate using the resin composition.

In the present invention, the unsaturated alkyd (5) 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 heptanoalcohol. It is obtained by dehydration condensation from a mixture of Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, and anhydrides thereof. Examples of unsaturated monocarboxylic acids include maleated synclopentadiene, 10-undecenoic acid, and the like. Examples of the saturated dicarboxylic acid include adipic acid, succinic acid, phthalic acid, isophthalic acid, terephthalic acid, and anhydrides thereof. Furthermore, these halogen-substituted derivatives,
Examples include chlorendic acid, tetrabromophthalic acid, tetrabromoterephthalic acid, and anhydrides thereof. Polyhydric alcohols include ethylene glycol,
Diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol, neopentyl glycol, hydrogenated bisphenol/L/
A, ethylene oxide and propylene oxide adducts of bisphenol A, epoxidized products of bisphenol, glycerin, pentaerythritol, and the like.

Examples include monoalcohols, hydroxylated synchropentagenes, cinnamyl alcohol, etc. Further, halogen-substituted derivatives thereof such as dibromoneopentyl glycol, ethylene oxide and propylene oxide adducts of tetrabromobisphenol A, and the like may also be mentioned.

Further, post-halogenated unsaturated alkyds, such as unsaturated alkyds 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 post-halides. In particular, from the viewpoint of heat softening resistance, molding workability, impact resistance, and flame retardancy, the bromine obtained by reacting an unsaturated alkyd with a maleated synchropentadiene, a polyhydric carboxylic acid, and a polyhydric alcohol, and then brominating it. 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, particularly 80 to 50 parts by weight. If it exceeds 90 parts by weight, the viscosity of the composition becomes too high, which reduces the tendency for workability to deteriorate and also reduces impact resistance.

The flexible monomer which is an essential component of the crosslinking monomer (B) in the present invention is represented by the following general formula.

I H2-C Coo R2-0+ C0Q(2CH2CH2CH2Q
(20-+tlRs (wherein R1 is hydrogen or methyl group,
R2 is a divalent aliphatic hydrocarbon group of 02-10, R3 is hydrogen or C, a hydrocarbon group of ~1°, and n is a positive integer of 1-20. ) 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. in particular,
ε-caprolactone adduct of hydroxyethyl (meth)acrylate, ε-caprolactone adduct of hydroxypropyl (meth)acrylate, hydroxybuty/L/
Examples include ε-caprolactone adducts of (meth)acrylates. Particularly preferred is an ε-caprolactone (8 mo/I/) adduct of hydroxyethyl methacrylate. 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). 0.1
If it is less than 50% by weight, the effect of improving impact resistance is small, and if it exceeds 50% by weight, the viscosity tends to increase or the rigidity decreases greatly. 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 those used for ordinary unsaturated polyethylene resins, and styrene is a typical example, but α-methylnutylene, vinyltoluene, chloronutylene, divinylbenzene, etc. Aromatic vinyl monomer, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
Acrylic acid esters such as hydroxyethyl acrylate, methacrylic acid esters such as methyl methacrylate, hydroxy-ethyl methacrylate, diallylphta 1
/-t, allyl compounds such as triallyl cyanurate, and the like.

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 and dialkyl peroxide peroxyesters provides particularly favorable results in terms of solder heat resistance, electrical insulation properties, and adhesive properties of the laminate. Examples of preferred organic peroxides c. Peroxyketals include 1.1-his(t-butylperoxyS/)-8. 8. Examples of dialkyl peroxides include di-t-butyl peroxide, and peroxyesters include t-butyl peroxybenzoate. These are used in an amount of about 0.5 to 2.0 parts based on the resin composition. In addition, the curing catalyst is not limited to these,
Known curing catalysts such as curing catalysts sensitive to light and curing catalysts sensitive to radiation and electron beams can also be used together with organic peroxides 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, flaxseed oil, and derivatives thereof. Examples of flame retardants include phosphorus-based flame retardants such as trioctylhonuphat, 1-rephenylphosphate, 1-recresylhonuphat, triphenylhonuphie), tris(chlorethyl)V) phosphate, and chlorinated paraffin. , tetrapromobisphenol/L/A1 tetrabromodiphenyl ether, etc., antimony compounds such as antimony trioxide and sodium antimonate, zinc borate, and aluminum hydroxide.

In addition, other polymers or fillers, acid value inhibitors,
Various additives such as lubricants and inorganic pigments can be included.

The unsaturated polyester resin composition of the present invention.

It can be used in the production of electrical laminates according to known methods. That is, an electrical laminate can be obtained by impregnating a base material with a resin composition, laminating a plurality of impregnated base materials, overlapping metal foil, and hardening and molding. As the base material, a glass base material such as glass cloth or glass mat, preferably a cellulone base material or a mixed base material thereof, etc. can be used, and particularly preferably, for example, kraft paper or linter paper can be used. For example, JP-A-56-98
It is preferable to pre-impregnate the substrate with the unsaturated polyester resin composition as described in No. 186 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 substantially no pressure conditions, as disclosed in JP-A-56-98186. That's 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, 196 g of maleic anhydride
g, water 889 to 1 equipped with a stirrer, thermometer, and reductor.
1. Place in a flask and heat at 120-140°C under nitrogen stream for 3 days.
The reaction was carried out for a period of time, and maleated synclopentadiene having an acid value of 226 was quantitatively obtained. This and 98 da maleic anhydride,
Ethylene glycol 94g, diethylene glycol/L7
111 da with xylene as a collinear solvent from 150 to 210°
C for 8 hours to obtain an unsaturated alkyd with an acid value of 19. The above unsaturated alkyd and methylene chloride 7671 were charged into a 21 flask equipped with a stirrer, a thermometer, and a dropping funnel with a side tube, stirred and dissolved, and then cooled to below 20°C with ice water.
Under a nitrogen stream, bromine 288f was added dropwise over 1.5 hours. After distilling off methylene chloride, 0.0% hydroquinone was added.
Styrene 395y containing 28 g was added to obtain a brominated unsaturated polyester having a styrene concentration of 28%. 47.5 parts of this brominated unsaturated polyester, soft unsaturated polyester (polymer/l/6820F, styrene content 87%,
Takeda Pharmaceutical Co., Ltd. 83 parts, aluminum hydroxide 10 parts
1 part, antimony trioxide 8.5 parts, organic peroxide curing catalyst (Perhexa 8M, manufactured by Nippon Oil & Fats Co., Ltd.), 1 part ε-caprolactone of hydroxyethyl methacrylate (8 mol)
Five parts of the adduct were sufficiently kneaded with a roll to obtain a flame retardant unsaturated polyester resin composition. This resin composition is impregnated into a methylolmelamine-treated paper base material, five sheets of the impregnated base material are laminated,
A laminate having a thickness of 1.551111 mm was obtained by heating and curing at 100'C for 15 minutes and at 1600C 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 was prepared in exactly the same manner as in the above example except that 5 parts of styrene was used instead of 5 parts of ε-caprolactone (8 mo/I/) adduct of hydroxyethyl methacrylate-1. A composition and a laminate were obtained. Table 1 shows the properties of the flame-retardant unsaturated polyester resin composition and the physical properties of the laminate.

From Table 1, it can be seen that the composition and laminate of the present invention have significantly improved impact strength and almost no increase in viscosity or decrease in rigidity.

Claims (1)

[Claims] 1. Unsaturated alkyd (N90 to 20 parts by weight and 01 to 50% by weight of the total amount of crosslinking monomers of the general formula % formula % (wherein, R1 is hydrogen or a methyl group, R2 is 02 to 1° divalent aliphatic hydrocarbon group, R3 is hydrogen or a C1 to 1o hydrocarbon group, n is a positive integer of 1 to 20). monomer (B) 10-8
0 parts by weight of an unsaturated polyester resin composition. 2. The unsaturated alkyd is a bromine-containing unsaturated alkyd obtained by reacting maleated dicyclopentadiene, a polycarboxylic acid, and a polyhydric alcohol, and then brominating the mixture, and a soft unsaturated alkyd for adjusting hardness. A composition according to claim 1, which is a mixture. 3. Unsaturated alkyd (A490-20 parts by weight, general formula % formula % of 01-50% by weight in the total amount of crosslinking monomers (in the formula, R1 is hydrogen or methyl group, R2 is 02-1°2 aliphatic hydrocarbon group, R3 is hydrogen or a hydrocarbon group of 01 to 10, and n is a positive integer of 1 to 20. ) 10-8
1. An electrical laminate obtained by laminating and curing a plurality of base materials impregnated with an unsaturated polyester resin composition comprising: 0 parts by weight. 4. A mixture of a bromine-containing unsaturated alkyd obtained by reacting mylenated dicyclopentadiene, a polyhydric carboxylic acid, and a polyhydric alcohol, and then brominating the unsaturated alkyd, and an unsaturated alkyd for hardness adjustment. An electrical laminate according to claim 8.