JPH0597964A - Rubber-modified vinyl ester resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in heat resistance and mechanical characteristics by reacting an epoxy resin with a specific conjugated butadiene-based polymer and (meth)acrylic acid and dissolving the resultant rubber-modified vinyl ester in a polymerizable monomer. CONSTITUTION:The objective inexpensive composition is obtained by dissolving (A) a rubber-modified vinyl ester prepared by reacting (i) an epoxy resin with (ii) a hydroxyl group-containing conjugated butadiene-based polymer prepared by carrying out reaction with an acid anhydride such as maleic anhydride and (iii) (meth)acrylic acid in (B) a polymerizable monomer such as styrene or vinyltolulene. The above-mentioned rubber-modified vinyl ester of the component (A) is preferably produced by using a polybasic acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rubber-modified vinyl ester resin composition, and more particularly to an inexpensive rubber-modified vinyl ester resin composition having excellent heat resistance and mechanical properties.

[0002]

2. Description of the Related Art Conventionally, thermosetting resins, especially radically polymerizable thermosetting resins represented by unsaturated polyesters,
It has a good balance of workability and curability during molding and heat resistance and mechanical properties after curing, and is widely used in various fields.
Among thermosetting resins, particularly vinyl ester resins have good heat resistance, water resistance, and mechanical properties, and as a fiber-reinforced composite material in combination with a reinforcing material such as glass fiber, for example,
It is widely used in ships, helmets, tanks, structural members such as leaf springs, insulating plates, and printed circuit boards for electrical applications. Resins used for electrical laminates such as insulating plates and electric circuit boards are required to have excellent water resistance, heat resistance, electrical characteristics, and impact resistance such as punching and mechanical strength.

A rubber-modified vinyl ether into which a rubbery copolymer is introduced is used as a resin having both of these properties. This rubber-modified vinyl ester is obtained, for example, by reacting a rubber-like copolymer having a carboxyl group or an amino group with an epoxy resin together with methacrylic acid and / or acrylic acid (hereinafter abbreviated as (meth) acrylic acid), or vinyl. It is obtained by reacting a rubbery copolymer having a group with an epoxy resin. However, the carboxyl group,
Since rubbery copolymers having functional groups such as amino groups and vinyl groups are generally expensive, there is a drawback that the cost becomes high.

[0004]

DISCLOSURE OF THE INVENTION The present invention eliminates the above-mentioned drawbacks of the prior art and includes a rubber-modified vinyl ester modified with an inexpensive hydroxyl group-containing rubber-like copolymer at low cost and in heat resistance and mechanical properties. An excellent rubber-modified vinyl ester resin composition is provided.

[0005]

The present invention is an epoxy resin.
(A), a hydroxyl group-containing conjugated butadiene polymer (B) obtained by reacting an acid anhydride, and a rubber-modified vinyl ester obtained by reacting acrylic acid and / or methacrylic acid (C) with a polymerizable monomer. The present invention relates to a rubber-modified vinyl ester resin composition that is dissolved.

Examples of the epoxy resin (A) used in the present invention include those represented by the general formula (1)

[Chemical 1] [In the formula, x is an integer in the range of 0 to 15]. Examples of commercially available products include Shell Chemical Co., Ltd. Epicoat 828, Epicoat 1001, Epicoat 1004, AER-664H and AER manufactured by Asahi Kasei Corporation.
-331, AER-337, D.W.
E. R. 330, D.I. E. R. 660, D.I. E. R. 6
64 etc. are mentioned.

A type in which a part of hydrogen atoms of the epoxy resin is replaced with halogen such as bromine can also be used. This commercially available product is Epotote YDB-4 manufactured by Tohto Kasei Co., Ltd.
00, YDB-340, Sumitomo Chemical Co., Ltd.
SB-340, ESB-400, ESB-500, ES
B-700, DER-542, DE manufactured by Dow Chemical Company
R-511, DER-580, etc. 104 manufactured by Yuka Shell Co., Ltd.
5, 1050, 1046, DX-248 and the like.

Further, the general formula (2)

[Chemical 2] An epoxy resin represented by the formula [wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group, and x is an integer in the range of 0 to 15] can also be used. This commercially available product is D.C. manufactured by Dow Chemical Company. E.
N. 431, D.I. E. N. 438, etc., Shell Chemical Co., Ltd. Epicoat 152, Epicoat 154, Ciba EPN1
138 and the like.

Union Carbide's ERL421
1 etc., CY208, CY221, CY manufactured by Ciba Geigy
350, XB2615, CY192, CY184, etc. are also used. These epoxy resins can be used alone or in combination of two or more kinds.

The hydroxyl group-containing butadiene-based copolymer (B) obtained by reacting the acid anhydride used in the present invention comprises a hydroxyl group-containing butadiene-based copolymer and an acid anhydride, for example, 70 to 140.
It can be obtained by reacting at a temperature of ℃ for 0.5 to 4 hours, but it is preferable to react the acid anhydride at a ratio of 0.8 to 1.2 molecule to one hydroxyl group of the hydroxyl group-containing butadiene-based copolymer. preferable. If the acid anhydride is less than 0.8 molecule per one hydroxyl group, the introduction of the hydroxyl group-containing butadiene-based copolymer into the vinyl ester may be incomplete and the heat resistance may be lowered, and the number exceeds 1.2 molecule. And unreacted acid anhydride remains, which reacts with the epoxy groups of the epoxy resin (A) to increase the molecular weight, which may cause gelation or increase in the viscosity of the rubber-modified vinyl ester.

The hydroxyl group-containing conjugated butadiene-based polymer is a known compound. For example, a conjugated diene-based monomer, a hydroxyl group-containing monomer and, if necessary, other monomers are copolymerized, It is obtained by polymerizing a system monomer or, if necessary, copolymerizing another monomer, and then introducing a hydroxyl group, for example, R-45HT manufactured by Idemitsu Atchem Co. is available. As the conjugated diene-based monomer, 1,3-butadiene, 2-chloro-1,3-butadiene, 2-cyano-
1,3-Butadiene, isoprene and the like are used. As the hydroxyl group-containing monomer, allyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like are used. Other monomers used as necessary include acrylonitrile, styrene, halogenated styrene, vinyltoluene,
Examples include various (meth) acrylic acid esters, dibasic acid esters, and allyl esters.

The molecular weight of the hydroxyl group-containing conjugated butadiene polymer is 1 in terms of the compatibility of the rubber-modified vinyl ester with the polymerizable monomer and the toughness of the cured product.
It is preferably about 000 to 50,000. From the viewpoint of toughness, heat resistance and compatibility, the amount of the hydroxyl group-containing conjugated butadiene-based polymer introduced into the vinyl ester is preferably 1 to 15% by weight based on the epoxy resin. As the acid anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride and the like are used. Of these, maleic anhydride is preferably used from the viewpoint of preventing the heat distortion temperature of the cured product from decreasing.

In the present invention, a polybasic acid can be used, if necessary, in the production of the rubber-modified vinyl ester. As the polybasic acid, it is preferable to use a dibasic acid having 12 or more carbon atoms. As such a commercially available product, SLB-12 (dodecanedioic acid) manufactured by Okamura Oil Co., Ltd.,
ULB-20 (mixture of isomers of unsaturated dibasic acid having 16 carbon atoms), SL-20 (mixture of saturated dibasic acid having 20 carbon atoms), tall oil having a carbon number of 36 and commonly referred to as dimer acid. Examples include dimerized fatty acid-based fatty acids such as Empor 1022, Empol 1024 (manufactured by Emery), Versadim 216, Versadim 288 (manufactured by Daiichi General Co.), and Haridimer # 200 (manufactured by Harima Chemical Industry).

By using the polybasic acid, the compatibility of the hydroxyl group-containing conjugated butadiene-based polymer with the epoxy resin can be improved, so that the modification amount of the vinyl ester can be increased. From the viewpoint of heat resistance, the amount of the polybasic acid used is preferably 15% by weight or less based on the rubber-modified vinyl ester. The rubber-modified vinyl ester used in the present invention is an epoxy resin (A), a hydroxyl group-containing conjugated butadiene-based copolymer (B) obtained by reacting an acid anhydride,
The (meth) acrylic acid (C) and the polybasic acid used as necessary are, for example, 60 to 150 ° C., preferably 70 to 150 ° C.
It is obtained by reacting all at once or at a temperature of 130 ° C. The amount of (meth) acrylic acid (C) used is preferably 0.8 to about the epoxy group of the epoxy resin.
The amount is 1.0 equivalent, and more preferably 0.9 to 1.0 equivalent. Further, for the reaction system, for example, an inert solvent such as toluene, xylene or ethyl acetate, a polymerizable monomer such as styrene, diallyl phthalate or (meth) acrylic acid ester can be used.

In the reaction, hydroquinone, parabenzoquinone and p-third group are used to prevent gelation due to polymerization.
It is preferable to use a polymerization inhibitor such as primary butyl catechol and hydroquinone monomethyl ether. In addition, quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, tertiary amines such as triethylamine and dimethylaniline, ferric chloride, lithium hydroxide, lithium chloride, and stannic chloride are used as the catalyst. You can also save time.

The polymerizable monomer used in the present invention is a compound containing at least one radically polymerizable unsaturated group in one molecule, such as styrene, vinyltoluene, divinylbenzene and methyl methacrylate. (Meth) acrylic acid esters such as methyl acrylate, ethyl methacrylate, ethyl acrylate, diallyl phthalate,
Examples thereof include allyl esters such as triallyl cyanurate, vinyl acetate, methacrylic acid, acrylic acid, etc. These may be used alone or in combination of two or more kinds.

The rubber-modified vinyl ester resin composition of the present invention is obtained by dissolving the rubber-modified vinyl ester in a polymerizable monomer. The amount of the polymerizable monomer used is preferably 25 to 100 parts by weight, more preferably 40 to 70 parts by weight, based on 100 parts by weight of the rubber-modified vinyl ester.
The rubber-modified vinyl ester resin composition can be cured under heating or at room temperature using an organic peroxide such as benzoyl peroxide, methyl ethyl ketone peroxide, tertiary butyl perbenzoate, cumene hydroperoxide as a curing catalyst. .. If necessary, a polyvalent metal salt such as cobalt naphthenate or cobalt octenoate or an aromatic amine such as dimethylaniline can be used as a curing accelerator.

[0018]

EXAMPLES The present invention will be described in detail below with reference to examples. In the examples, parts and% mean parts by weight and% by weight. Example 1 2400 parts of a hydroxyl group-containing conjugated butadiene-based polymer R-45HT (hydroxyl value 47, manufactured by Idemitsu Atchem Co., Ltd.) and 200 parts of maleic anhydride were placed in a 3 liter flask equipped with a stirrer and a thermometer, and heated to 100 with a mantle heater. The mixture was kept at 0 ° C. and reacted for 2 hours to obtain a hydroxyl group-containing conjugated butadiene polymer (I) reacted with an acid anhydride having an acid value of 41.

Then, in a 2 liter flask equipped with a stirrer, a thermometer and an air blowing tube, Ep-828 (bisphenol type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) 96
6 parts, 107 parts of a hydroxyl group-containing conjugated butadiene-based copolymer (I) reacted with an acid anhydride, 427 parts of methacrylic acid, 0.5 part of hydroquinone and 3.0 parts of trimethylbenzylammonium chloride were charged, and a mantle heater was used for 115 The reaction was carried out while keeping the temperature at ℃. After reacting for 6 hours, a rubber-modified vinyl ester having an acid value of 4 was obtained. This rubber-modified vinyl ester was dissolved in 1000 parts of styrene to obtain a rubber-modified vinyl ester resin composition (I). Next, 5 parts were added to 100 parts of the rubber-modified vinyl ester resin composition (I).
After 4 parts of 0% benzoyl peroxide powder was added and well dissolved, it was poured into a mold and cured at 100 ° C. for 2 hours and then at 120 ° C. for 2 hours to obtain a resin cured product having a thickness of 3 mm. Regarding the obtained cured product, JISK 7113
In accordance with the above, a tensile test was carried out to measure the tensile strength and elongation, and the glass transition temperature was measured by a thermomechanical analyzer type 8140C (manufactured by Rigaku Denki Co., Ltd.). The results are shown in Table 1.
Shown in.

Example 2 In a flask similar to that of Example 1, 107 parts of the hydroxyl group-containing copolymer (I) obtained by reacting the acid anhydride obtained in Example 1 with Ep was added.
-828 and 966 parts were charged, 3.0 parts of trimethylbenzylammonium chloride was further added, and the mixture was reacted using a mantle heater at 100 ° C for 2 hours until the acid value became 0.5. Next, 427 parts of methacrylic acid and 0.5 part of hydronoquinone were added thereto, and further reacted at 110 ° C. for 5 hours to obtain a rubber-modified vinyl ester having an acid value of 3.
1000 parts of styrene was added to this rubber-modified vinyl ester and well dissolved to obtain a rubber-modified vinyl ester resin composition (II). This resin was cured in the same manner as in Example 1, and the tensile test and the glass transition temperature were measured. The results are shown in Table 1.

COMPARATIVE EXAMPLE 1 The reaction was carried out in the same manner as in Example 1 except that the hydroxyl group-containing conjugated butadiene copolymer (I) reacted with an acid anhydride was not used, and a vinyl having an acid value of 5 was used. The ester was obtained. Further, this vinyl ester was dissolved in 600 parts of styrene to obtain a vinyl ester resin composition (i), which was cured in the same manner as in Example 1, and a tensile test and a glass transition temperature were measured. The results are shown in Table 1.

Example 3 Using the flask of Example 1, Ep-828, 809 parts,
162 parts of a hydroxyl group-containing conjugated butadiene-based copolymer (I) obtained by reacting the acid anhydride obtained in Example 1, and halidimer # 2
00 (dimer acid, Harima Chemical Industry Co., Ltd.) 248 parts, methacrylic acid 282 parts, hydroquinone 0.5 part and trimethylbenzylammonium chloride 3.0 parts were added and reacted at 110 ° C. to give an acid value of 5 in 8 hours. A rubber-modified vinyl ester was obtained. This rubber-modified vinyl ester was dissolved in 1000 parts of styrene to obtain a rubber-modified vinyl ester resin composition (III), which was cured in the same manner as in Example 1 and subjected to a tensile test and a glass transition temperature measurement. The results are shown in Table 1.

Comparative Example 2 Reaction was performed in the same manner as in Example 3 except that the hydroxyl group-containing conjugated butadiene copolymer (I) reacted with an acid anhydride was replaced with dimer acid, and after 8 hours, Since the acid value became constant at about 20, the reaction was terminated. This reaction product was dissolved in 1000 parts of styrene to obtain a vinyl ester resin composition (II). It was cured in the same manner as in Example 1, and the tensile test and the glass transition temperature were measured. The results are shown in Table 1.

[0024]

[Table 1] From Table 1, in Examples 1 and 2, the elongation is high and the toughness is excellent even though the glass transition temperature is almost the same as that of Comparative Example 1, and in Example 3, the elongation and the toughness are the same as those of Comparative Example 2. It is shown that the heat resistance is significantly improved although the values are almost the same.

[0025]

According to the rubber-modified vinyl ester resin composition of the present invention, a cured product having excellent heat resistance and mechanical properties can be obtained, and a rubber-modified vinyl ester modified with an inexpensive hydroxyl group-containing conjugated butadiene polymer is obtained. Is used,
Cost reduction can be achieved.

Claims (2)

[Claims] 1. A rubber-modified vinyl ester obtained by reacting an epoxy resin (A), a hydroxyl group-containing conjugated butadiene polymer (B) reacted with an acid anhydride, and acrylic acid and / or methacrylic acid (C). A rubber-modified vinyl ester resin composition obtained by dissolving in a polymerizable monomer. 2. A rubber-modified vinyl obtained by dissolving a rubber-modified vinyl ester obtained by reacting (A), (B), (C) according to claim 1 and a polybasic acid in a polymerizable monomer. Ester resin composition.