JP3321078B2 - Resin composition and cured resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition.

[0002]

2. Description of the Related Art Unsaturated polyester resins are used in various fields as useful molding materials because of their good workability at the time of molding, heat resistance and corrosion resistance of molded products, and their advantages of being lighter than metals. Have been.

[0003] However, while having such features,
Lack of impact resistance and toughness, one of the factors is
Since the cured product has a three-dimensional structure, it is considered that the cushioning property against external force such as impact is poor. In order to improve this, a method of blending a rubbery polymer or the like with an unsaturated polyester resin has been studied so far. For example, blending of a butadiene-acrylonitrile copolymer has been attempted.

[0004] However, in this method, the compatibility between the unsaturated polyester and the butadiene-acrylonitrile copolymer is poor, so that the separation of the composition in a liquid state occurs in a short time, and there is a large problem in storage stability.
There is also a problem in terms of characteristics that impact resistance cannot be expressed with good reproducibility.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a resin capable of achieving an improvement in impact resistance, toughness and storage stability while maintaining the features of a molded product such as heat resistance and corrosion resistance. The development of the composition was raised as an issue.

[0006]

The resin composition of the present invention comprises:
Unsaturated polyester (A) derived using an alkylene oxide adduct of tetrabromobisphenol represented by the formula 1 as a glycol component, butadiene containing at least one bisphenol skeleton represented by the formula 2 in the molecule;
The gist is that it comprises the acrylonitrile copolymer (B) and the radically polymerizable unsaturated monomer (C).

[0007]

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[0008]

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A butadiene-acrylonitrile copolymer having a bisphenol skeleton represented by Formula 2 is blended with an unsaturated polyester resin derived by using an alkylene oxide adduct of tetrabromobisphenol represented by Formula 1 as a glycol component. As a result, the storage stability in a liquid state was improved, and a phase-separated state was not obtained even after a long period of time. Further, impact resistance, toughness and other physical properties of the cured product were well balanced, and a resin composition was obtained. .

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention is an unsaturated polyester (A) derived by using an alkylene oxide adduct of tetrabromobisphenol represented by the formula 1 as a glycol. Butadiene-acrylonitrile copolymer (B) containing one or more bisphenol skeletons, and a radical polymerizable unsaturated monomer (C).

[0011]

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[0012]

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The unsaturated polyester (A) of the present invention is obtained by an esterification reaction of a glycol component represented by the formula 1 alone or mixed with another known glycol, and a carboxylic acid component.

Here, the alkylene oxide adduct of tetrabromobisphenol represented by the formula 1 is preferably used in a proportion occupying 15 mol% or more of the total glycol component. If this ratio is less than 15 mol%, the storage stability is reduced, and turbidity and phase separation may occur.

[0015] The esterification reaction can be carried out according to a method known in the art. For example, as a typical method, each component is placed under an inert gas atmosphere such as nitrogen gas.
In the presence or absence of a water azeotropic solvent such as toluene or xylene, or an esterification catalyst such as tin oxalate, 120-
A method of heating to a temperature range of 250 ° C., preferably 150 to 220 ° C., and performing dehydration condensation until a desired molecular weight is obtained.

Glycols used as a mixture include:
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, hydrogenated bisphenol A, bisphenol A
Can be appropriately selected from glycols known in the unsaturated polyester industry such as alkylene oxide adducts.

The carboxylic acid component contains an α, β-unsaturated dicarboxylic acid component as an essential component.
The β-unsaturated dicarboxylic acid component can be appropriately selected from those known in the art, such as maleic anhydride, fumaric acid, and itaconic acid, and used. Examples of the saturated dicarboxylic acid include phthalic acid, halogenated phthalic acid, isophthalic acid, terephthalic acid, succinic acid, dimer acid, adipic acid, sebacic acid, tetrahydrophthalic acid, and 3,6-
A dicarboxylic acid known in the art, such as endmethylenetetrahydrophthalic acid or an acid anhydride thereof, can be appropriately selected and used.

The unsaturated polyester (A) thus obtained can be used alone in the same manner as a conventionally known unsaturated polyester, and gives a cured resin having heat resistance, corrosion resistance and the like. In the invention, a butadiene-acrylonitrile copolymer (B) containing at least one of the following bisphenol skeletons is essential for solving the problem.

In the present invention, the butadiene-acrylonitrile copolymer (B) containing one or more bisphenol skeletons in the molecule is one containing one or more bisphenol skeletons represented by the formula 2 in the molecule: Specifically, a bisphenol type epoxy resin (B1) represented by Formula 3
And a butadiene-acrylonitrile copolymer (B2) having an amino group and / or a carboxyl group.

[0020]

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In the present invention, acrylic acid and / or methacrylic acid are used together in the reaction of the bisphenol type epoxy resin (B1) with the butadiene-acrylonitrile copolymer (B2) having an amino group and / or a carboxyl group. A butadiene-acrylonitrile copolymer containing one or more bisphenol skeletons and (meth) acryloyl groups in the molecule can also be used.

In each case, the number of epoxy groups in B1: B2
Number of amino groups and / or carboxyl groups in the product = 1:
By reacting at a ratio of 2 to 2: 1, a compound containing at least one of a bisphenol skeleton and a butadiene-acrylonitrile copolymer skeleton in one molecule is obtained as a main component, which is suitable for the purpose of the present invention. I have.

Here, a bisphenol-type epoxy resin (B1) and a butadiene-acrylonitrile copolymer (B2) having an amino group and / or a carboxyl group are used.
In the reaction of only B1, if the number of epoxy groups in B1 is increased, the epoxy group terminal is mainly obtained. Conversely, if the number of amino groups and / or carboxyl groups in B2 is increased, amino groups and / or carboxyl groups are increased. Carboxyl-terminated ones are mainly obtained. Further, a bisphenol-type epoxy resin (B1) and a butadiene-acrylonitrile copolymer having an amino group and / or a carboxyl group (B2)
Further, when the reaction is further carried out using acrylic acid and / or methacrylic acid, those having a (meth) acryloyl group terminal are mainly obtained, and any of these can be used in the present invention.

These reactions can be carried out according to a conventionally known method for producing a vinyl ester resin. Examples of the esterification catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, phosphorus compounds such as triphenylphosphine, and organic acids of metals. The reaction may be carried out at 80 to 130 ° C. using a salt, an inorganic salt of a metal, a chelated metal or the like in the presence of a polymerization inhibitor such as hydroquinone or oxygen. In the above method, a solvent (e.g., an inert solvent such as toluene, xylene, methyl isobutyl ketone, or ethyl acetate, styrene, α-methylstyrene,
Radical polymerizable unsaturated monomers such as diallyl phthalate and alkyl (meth) acrylate described below) can coexist.

The radical polymerizable unsaturated monomer (C) in the present invention includes styrene, α-methylstyrene, α
-Aromatic vinyl monomers such as chlorostyrene, vinyltoluene, divinylbenzene, diallylphthalate, and diallylbenzenephosphonate; vinyl ester monomers such as vinyl acetate and vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate; Butyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [ 2- (meth) acryloyloxyethyl]
(Meth) acrylic monomers such as triazine; triallyl cyanurate; and the like, and one or more of these can be used.

The resin composition of the present invention comprises the above-mentioned unsaturated polyester (A), butadiene-acrylonitrile copolymer (B), and radically polymerizable unsaturated monomer (C). However, by using an unsaturated polyester (A) derived by using an alkylene oxide adduct of tetrabromobisphenol represented by the formula 1 in a proportion occupying 30 mol% or more of the total glycol component, electric-related applications and the like can be obtained. Flame retardant resin composition useful for

When the resin composition of the present invention is actually cured and used, a (thermal or optical) polymerization initiator is used.

Known thermal polymerization initiators can be used, and specific examples thereof include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, and t.
-Butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, t-
Organic peroxides such as butylperoxybenzoate and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile are exemplified. In addition, a curing accelerator may be mixed and used at the time of thermal polymerization, and examples of the curing accelerator include cobalt naphthenate and cobalt octylate, and tertiary amines. The thermal polymerization initiator is preferably used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the resin composition.

As the photopolymerization initiator usable in the present invention, known photopolymerization initiators can be used. Specifically, benzoin such as benzoin, benzoin methyl ether and benzoin ethyl ether and their alkyl ethers; acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-
Acetophenones such as butyldioxy-1-methylethyl) acetophenone; 2-methylanthraquinone;
Anthraquinones such as amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone;
Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) ) Benzophenones such as benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 -One and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides and xanthones.

These photopolymerization initiators are used as one kind or as a mixture of two or more kinds, and preferably 0.5 to 30 parts by weight based on 100 parts by weight of the resin composition.

The resin composition of the present invention can be used by mixing other known radically polymerizable resins such as unsaturated polyesters and vinyl esters. In addition, a releasing agent, a lubricant, a plasticizer, an oxidizing agent, Inhibitors, ultraviolet absorbers, flame retardants, polymerization inhibitors, fillers, thickeners, pigments, and other known additives may be used depending on the application. Further, various reinforcing fibers can be used as reinforcing fibers to obtain a fiber-reinforced composite material.

The use of the resin composition of the present invention for obtaining a cured product of the composition is the most preferred method for the purpose of the present invention. In particular, it is useful as a casting resin or a matrix resin for fiber-reinforced composite materials, and is used as a sealing material that requires impact resistance and crack resistance, as an automobile part or large-sized structural material, or as a material with heat resistance, toughness, and electrical properties. It can be used for an electric printed wiring board, an insulating plate, etc., which require a high balance of physical properties such as.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the present invention, and all modifications and alterations that do not depart from the gist of the present invention are within the technical scope of the present invention. Is included. The parts in the examples are on a weight basis.

Reference Example 1 (Unsaturated polyester tree for the example )
Fat [A-1]) In a flask equipped with a stirrer, reflux condenser, gas inlet tube and thermometer, 0.2 mol of an adduct obtained by adding 2 mol of propylene oxide to 1 mol of tetrabromobisphenol A, 0.83 mol of propylene glycol and 1 mol of fumaric acid were added and reacted at 185 ° C. in a nitrogen stream to synthesize unsaturated polyester [A-1]. 60 parts of this unsaturated polyester, 40 parts of styrene, and 0.01 part of hydroquinone were mixed to obtain a mixture of unsaturated polyester resin [A-1] and styrene.

Reference Example 2 (Unsaturated polyester tree for the example )
Fat [A-2]) In the same manner as in Reference Example 1, tetrabromobisphenol A
An unsaturated polyester [A-2] was synthesized by reacting 0.5 mol of an adduct obtained by adding 2 mol of propylene oxide to 1 mol, 0.53 mol of dipropylene glycol, and 1 mol of fumaric acid. This unsaturated polyester 6
0 parts, 40 parts of styrene, and 0.01 of hydroquinone
Were mixed to obtain a mixture of unsaturated polyester resin [A-2] and styrene.

Comparative Reference Example 1 (Unsaturated polyester for comparative example)
Resin [A'-1]) In Reference Example 2, bisphenol A was used instead of tetrabromobisphenol A adduct of propylene oxide.
Unsaturated polyester [A'-1] was synthesized in the same manner except that 0.5 mol of an adduct obtained by adding 2 mol of propylene oxide to 1 mol was used. 60 parts of this unsaturated polyester, 40 parts of styrene, and 0.01 part of hydroquinone were mixed to obtain a mixture of a comparative unsaturated polyester resin [A'-1] and styrene.

Reference Example 3 (butadiene-acrylo for example )
Nitrile copolymer [B-1]) A flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer is charged with a brominated bisphenol A type epoxy resin YD.
B-400 (manufactured by Toto Kasei, epoxy equivalent 400) 800
Part and liquid acrylonitrile butadiene rubber containing terminal carboxyl group (“Hiker CTBN1300 × 13”: BFGoo
drich Chemical Company, carboxyl equivalent 1892) 18
92 parts, 86 parts of methacrylic acid, 1852 parts of styrene, 13.9 parts of triethylamine and 1.4 parts of hydroquinone were added and reacted at 110 ° C. while introducing air to give a butadiene-acrylonitrile copolymer [B- 1]
And a mixture of styrene.

Reference Example 4 (butadiene-acrylo
Nitrile copolymer [B-2]) Using the same apparatus as in Reference Example 3, 370 parts of bisphenol A type epoxy resin GY-250 (manufactured by Ciba Geigy, epoxy equivalent: 185) and the terminal carboxyl used in Reference Example 3 1892 parts of a group-containing liquid acrylonitrile butadiene rubber (“Hiker CTBN1300 × 13”), 1508 parts of styrene, 11.3 parts of triethylamine and 1.1 parts of hydroquinone were added, and reacted at 110 ° C. while introducing air. A mixture of butadiene-acrylonitrile copolymer [B-2] and styrene was obtained.

Comparative Reference Example 2 (butadiene-ac
Lilonitrile copolymer [B'-1]) The liquid acrylonitrile-butadiene rubber having a terminal carboxyl group used in Reference Example 3 (“Hiker CTBN1300 × 1
3 ") was directly used as a butadiene-acrylonitrile copolymer for comparative example [B'-1], and 60 parts of this and 40 parts of styrene were mixed.

(Examples 1 to 4 and Comparative Examples 1 to 4) The mixtures obtained in Reference Examples 1 to 4 and Comparative Reference Examples 1 and 2 are shown in Table 1.
The following evaluation was performed using the composition shown in Table 1. Table 2 shows the results
Shown in

<Stability in liquid state> Each mixture is φ18 mm
In a Pyrex test tube, and allowed to stand at room temperature for 24 hours to compare the stability (presence or absence of separation).

<Physical Properties of Cured Product> 0.3 parts of cobalt octenoate (metal content: 8% by weight) and 1.5 parts of methyl ethyl ketone peroxide (peroxide content: 55% by weight) were added to each resin solution. I got The following evaluation was performed on a flat plate obtained by curing these between two glass plates (thickness: 3 mm).

Fracture toughness A test piece having the size shown in FIG. 1 was prepared, and a starter crack was inserted with a razor at the end of the center notch, and then 10 mm.
A load-time curve (FIG. 2) was obtained at a speed of / min, and a fracture toughness value was calculated from the load (Pc) at the time of fracture, the length of the crack (a), and the like according to Formula 1.

[0044]

(Equation 1)

Load deflection temperature HDT & VSPTT manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K6911
Measured using ESTER.

Combustion Test A cured product obtained from the blends of Examples 3 and 4 in Table 1 was subjected to a combustion test in accordance with "UL-94", and was found to be equivalent to V-0.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

According to the present invention, it is possible to obtain a resin composition having good cured product characteristics such as heat resistance, corrosion resistance, impact resistance, and toughness, and also having improved storage stability in a liquid state before curing. Was.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a cured test piece for measuring a fracture toughness value.

FIG. 2 is a load-time curve when a fracture toughness value is measured.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 67/06 C08L 67/06 (72) Inventor Kento Toba 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (56) References JP-A-4-300911 (JP, A) JP-A-2-212544 (JP, A) JP-A-63-105011 (JP, A) JP-A-60-84350 (JP, A) JP-A-54-56692 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 283/01 C08F 290/00-290/14 C08F 299/00-299/08 C08G 59 / 00-59/72 C08L 1/00-101/16

Claims (5)

(57) [Claims] 1. A type total glycol component tetrabromobisphenol alkylene oxide adduct represented by 1
Unsaturated polyester (A) derived by using a proportion of at least 15 mol% of butadiene-acrylonitrile copolymer (B) containing at least one bisphenol skeleton represented by Formula 2 in the molecule
And a bisphenol-type epoxy resin represented by the following formula 3:
Fatty acid (B1), amino group and / or carboxyl group
Butadiene-acrylonitrile copolymer (B)
2) and the bisphenol type epoxy resin (B1)
And the number of epoxy groups of butadiene-acrylonitrile
Amino group and / or carboxyl group of copolymer (B2)
The reaction is carried out at a ratio of 1: 2 to 2: 1 with the number of sil groups.
Butadiene-acrylonitrile copolymer obtained
(B) and a radically polymerizable unsaturated monomer (C).
A resin composition having excellent storage stability . Embedded image Embedded image Embedded image 2. The butadiene-acrylonitrile copolymer
The compound (B) is a bisphenol-type ester represented by the above formula (3).
Epoxy resin (B1) and amino group and / or carboxy
Butadiene-acrylonitrile copolymer having xyl group
Body (B2) is the bisphenol type epoxy resin
The number of epoxy groups of (B1), the butadiene - acrylic
Amino group of lonitrile copolymer (B2) and / or
The ratio of the number of carboxyl groups is 1: 2 to 2: 1.
And acrylic acid and / or methacrylic acid
(Meth) acryloyl group-containing butadiene reacted with acid
2. The storage according to claim 1, which is an acrylonitrile copolymer.
A resin composition with excellent storage stability. 3. The method of claim 1, wherein the tetrabromobisphenol is tetrabu.
3. The method according to claim 1, which is rombisphenol A.
A resin composition having excellent storage stability. 4. An unsaturated polyester (A) having the formula 1
The alkylene of tetrabromobisphenol represented by
Add 30% by mole or more of the total glycol component
4. The method according to claim 1, which is derived by using the occupying ratio.
The resin composition according to any one of the above, which is excellent in storage stability. 5. The method according to claim 1, wherein the radically polymerizable unsaturated monomer (C) is
Storage stability according to any one of claims 1 to 4, which is styrene.
A resin composition with excellent properties.