JPS63122719A - Radically curable resin composition and laminate therefrom - Google Patents

Abstract

PURPOSE:To obtain the titled composition with markedly improved impact resistance, free from decrease in rigidity, useful for laminates for electrical circuit, by blending a side chain double bond type resin and a crosslinking monomer component containing a flexibilizing monomer of specific structure. CONSTITUTION:The objective composition can be obtained by blending (A) 90-10pts.wt. of a side chain double bond type resin and (B) 10-90pts.wt. of a crosslinking monomer component containing (i) 0.1-40wt% of a flexibilizing monomer of formula (R1 is H or methyl; R2 is 2-5C divalent aliphatic hydrocarbon; R3 is H or 1-10C hydrocarbon; n is 1-15) (pref., hydroxyethyl (meth) acrylate epsilon-caprolactone adduct) and (ii) another monomer (pref. styrene).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a radically curable resin composition with improved impact resistance and a circuit laminate using the resin composition.

[Conventional technology] Conventionally, unsaturated polyester resins have been typical as radical curable resins, but although they have relatively good physical properties and moldability, they have extremely poor impact resistance. , it is severely limited in its field of application.

Therefore, various improvements have been made to improve the impact resistance of unsaturated polyester resins.

For example, a method of modifying an unsaturated polyester resin using an acid or alcohol with a long alkyl chain as one component, a method of adding a polybutadiene rubber as one component, etc. have been used.

However, even though all of the above methods can improve impact resistance,
This results in a significant loss of the properties inherent to the unsaturated polyester resin, making it difficult to call this a practical method.

In addition, the method disclosed in Japanese Patent Application Laid-open No. 60-6715 is 1.
In order to improve the impact resistance of unsaturated polyester resins, flexibility-imparting monomers having long-chain hydrocarbon substituents are used in combination, but the problem has not yet been fully resolved.

[Problems to be Solved by the Invention] In view of the current situation, the present invention provides a radically curable resin composition that fully exhibits the inherent performance of a matrix resin and has excellent impact resistance, and the curable resin composition. The purpose is to provide electrical laminates using materials.

[Means for Solving the Problems] The object of the present invention is to obtain a side chain double bond type resin (A) 90
~101ffi1. ! 'E,/' for mII? -(B)
10 to 90 parts by weight of a radically curable resin composition, wherein the total amount of crosslinking monomers contains 0.1 to 40 parts by weight.
[In the formula, R1 is hydrogen or a methyl group, R2 is a C divalent aliphatic hydrocarbon group, R3 is water 2 to 5 atoms or a C hydrocarbon group, n is 1 ~15 positive integers from 1 to 10. ] This is achieved by a radically curable resin composition containing the flexibility-imparting monomer as an essential component, and an electrical laminate using the resin composition.

[Function] The side chain double bond type resin referred to in the present invention refers to a main chain obtained by polymerization of a monovinyl compound, and a methacryloyl group or an acryloyl group at the end of the side chain [hereinafter, both are referred to as a (meth)acryloyl group. ” refers to a curable resin consisting of a side chain containing

Among the monovinyl compounds constituting the main chain of the side chain double bond type resin in the present invention, styrene, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester,
Included are acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, maleic anhydride, maleic ester, glycidyl methacrylate, glycidyl acrylate, allyl alcohol, butadiene, hydroxyethyl methacrylate-1, and the like.

In the present invention, these are used in combination as a copolymer.

In the present invention, various methods can be employed to introduce a side chain having a double bond at the end of the side chain into the polymer constituting the main chain. Some examples are as follows.

(1) React one epoxy group of a compound having a jepoxy group such as a bisphenol type diglycidyl ether type epoxy group with the carboxyl group of the side chain,
The remaining epoxy group is reacted with (meth)acrylic acid.

(2) React the side chain carboxyl group with glycidyl (meth)acrylate.

(3) React the epoxy group of the side chain with (meth)acrylic acid.

(4) A diisocyanate compound is reacted with hydroxyethyl (meth)acrylate to create a reaction product containing monoisocyanate as the main component and almost no diisocyanate compound, and the isocyanate groups contained in this reaction product are combined with the hydroxyl groups of the main chain polymer. Make it react.

In the exemplified method, the main chain was copolymerized first, but in the present invention, of course, the reaction to form the side chain is carried out first, and such monomers are finally copolymerized to form the side chain terminal (method). ) A side chain double bond type resin containing an acryloyl group may be produced.

In the present invention, the usage amount of the side chain double bond type resin is determined based on the purpose,
Although it can be varied depending on the intended use, it is preferably 90 to 10 parts by weight, particularly 80 to 20 parts by weight. When the amount exceeds 90 parts by weight, the cured product tends to become hard and brittle, and when it is less than 10 parts by weight, the curability tends to decrease.

The side chain double bond type resin used in the present invention has a well-balanced thermoplastic resin-like property due to the characteristics of its skeletal structure and rigidity resulting from the three-dimensional crosslinking of the side chain double bonds, and is unique to unsaturated polyester resins. It has excellent impact resistance that cannot be achieved. Furthermore, other physical properties are not inferior to unsaturated polyester resins. By using such a side chain double bond type resin together with the flexibility-imparting monomer shown below, a curable resin composition with significantly improved impact resistance and excellent other physical properties can be obtained.

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

■ COO-R2-0+ COCH2CH2Cl12C12
CH20÷oR3 (wherein, R1 is hydrogen or a methyl group, R
2 is a divalent aliphatic hydrocarbon group of 02 to 5, R3 is hydrogen or a hydrocarbon group of 01 to 1o, and n is a positive integer of 1 to 15. ] Such a flexibility-imparting monomer is typically obtained by reacting (meth)acrylic acid with ethylene oxide, propylene oxide, or tetrahydrofuran, followed by an addition reaction with ε-caprolactone.

Specific examples thereof include ε-caprolactone adducts of hydroxyethyl (meth)acrylate and ε-caprolactone adducts of hydroxypropyl (meth)acrylate.

The amount of the flexibility-imparting monomer used in the crosslinking monomer (8) is in the range of 0.1 to 40% by weight based on the total amount of (B). 0
．． If it is less than 1%, the effect of improving 1 Will resistance is small, and 4
If it exceeds 0%, the stiffness will be significantly lowered.

Other crosslinking monomers (8) may be those used in ordinary unsaturated polyester resins, and styrene is a typical example, but other crosslinking monomers (8) include α-methylstyrene, vinyltoluene, chlorostyrene, and divinylbenzene. , acrylic esters, methacrylic esters,
Examples include diallyl phthalate and triallyl cyanurate.

The resin composition of the present invention can be cured using a general-purpose organic peroxide. Further, 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 radically curable resin composition of the present invention may contain additives such as plasticizers, flame retardants, fillers, stabilizers, lubricants, inorganic pigments, reinforcing materials, colorants, mold release agents, accelerators, etc. as necessary. Various additives can be included.

The radically curable resin composition of the present invention can be used to produce circuit laminates according to known methods. In other words, 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 coated with adhesive is layered on one or both sides, and then hardened and molded. A laminate can be obtained.

As the base material, a glass base material such as a glass cloth or a glass mat, a cellulose base material, or a mixed base material thereof can be used.

The m-layer board using the resin composition of the present invention has excellent impact resistance, good rigidity, and heat resistance.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples unless it departs from the gist of the present invention.

Throughout this specification, temperatures are expressed in degrees Celsius, and parts and percentages are on a one-base basis unless otherwise specified.

Example 1 Styrene (300 g) and glycidyl methacrylate (45,
4g), benzoyl peroxide (3.5g), and n-dodecylmercaptan (3.5g). Styrene (133 g), glycidyl methacrylate (45.4 g), benzoyl peroxide (1.8 g), n-dodecyl mercaptan (1
, 8 g) was added dropwise, and the mixture was further reacted at 115° C. for 1.5 hours. As a result, the reaction rate of styrene was 48%, the reaction rate of glycidyl methacrylate was 76%, and a colorless and transparent copolymer solution was obtained.

Acrylic in this solution! (49.0 g) and hydroquinone (0.5 g) were added and reacted at 100° C. for 4 hours. The reaction rate of acrylic acid was 90%, and a pale yellow transparent resin solution (I) was obtained.

[Manufacture of laminates]

The above resin solution (I) (75 parts), 2゜3-dibromopropyl maleate (25 parts), antimony trioxide (4 parts)
, a specific peroxide catalyst [Barhexa 3MJ (trade name, manufactured by NOF Corporation) (1 part), and an adduct of ε-caprolactone (8 mol) of hydroxyethyl methacrylate (5 parts) were thoroughly mixed, and a radical A curable resin composition was obtained. This resin composition is impregnated into a methylolmelamine-treated paper base material,
Five impregnated substrates were laminated and cured by heating at a pressure of 0.1 to 9/cd G for 15 minutes at 100°C and 10 minutes at 160°C to obtain a laminate with a thickness of 1.60 M.

Table 1 shows the properties of the curable resin composition and the physical properties of the laminate.

Comparative Example 1 [Production of unsaturated polyester resin] Propylene glycol (
100g>, isophthalic acid (83,29>) was charged,
185℃3 while distilling condensed water under nitrogen blowing conditions.
Allowed time to react. Next, fumaric acid (87.2 g) was added and reacted at 185° C. for 6 hours. Finally, about 10III inside the system
The pressure was reduced to IHg, and the temperature inside the flask was raised to 200°C to complete the reaction, and a resin with an acid value of 30 was obtained. This resin was dissolved in styrene to obtain an unsaturated polyester resin (II) having a styrene concentration of 40%.

[Manufacture of laminates]

A curable resin composition and a laminate were obtained in exactly the same manner as in the above example except that the unsaturated polyester resin (n) (75 parts) was used instead of the resin solution (I) (75 parts). The properties of the curable resin composition and the physical properties of the laminate are listed in Table 1.

Table 1 [Effects of the Invention] Table 1 shows that the composition and laminate of the present invention have significantly improved impact strength and almost no decrease in rigidity.

Claims (2)

[Claims] (1) A radically curable resin composition comprising 90 to 10 parts by weight of a side chain double bond type resin (A) and 10 to 90 parts by weight of a crosslinking monomer (B), which is based on the total amount of the crosslinking monomer. General formula of 0.1 to 40% by weight ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 is hydrogen or methyl group, R_2 is C_2_
～_5 divalent aliphatic hydrocarbon group, R_3 is hydrogen or C
The hydrocarbon group of _1_ to _1_0, n means a positive integer of 1 to 15. ] A radically curable resin composition containing a flexibility-imparting monomer as an essential component. (2) A radically curable resin composition comprising 90 to 10 parts by weight of a side chain double bond type resin (A) and 10 to 90 parts by weight of a crosslinking monomer (B), which is based on the total amount of the crosslinking monomer. General formula of 0.1 to 40% by weight ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 is hydrogen or methyl group, R_2 is C_2_
～_5 divalent aliphatic hydrocarbon group, R_3 is hydrogen or C
The hydrocarbon group of _1_ to _1_0, n means a positive integer of 1 to 15. ] An electrical laminate formed by laminating and curing a plurality of base materials impregnated with a radically curable resin composition containing the flexibility-imparting monomer as an essential component.