JPS6084350A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a corrosion-resistant, heat-resistant resin compsn. having excellent flame retardance, by blending a bromine-contg. epoxy poly(meth)acrylate, an unsaturated polyester and a polymerizable unsaturated monomer. CONSTITUTION:A resin compsn. having a bromine content of 15-30wt% [8- 16wt% thereof being originated from a bromine-contg. epoxy poly(meth)acrylate (component a)] consists of 100pts.wt. bromine-contg. epoxy poly(meth)acrylate (a) obtd. by reacting a bromine-contg. epoxy resin with an acid component mainly composed of (meth)acrylic acid, 20-120pts.wt. unsaturated polyester (b) obtd. by reacting an alcohol component (i) contg. at least 50mol% of a compd. of the formula with an acid component (ii) contg. at least 50mol% of an alpha,beta-unsaturated dicarboxylic acid and/or its anhydride, 30-150pts.wt. polymerizable unsaturated monomer (c) and optionally 0-50pts.wt. flame retarder (d).

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] This invention relates to a corrosion-resistant and heat-resistant resin composition with excellent flame retardancy.

[Background technology]

Thermosetting resins, especially radical polymerizable thermosetting resins such as unsaturated polyester resins, have a good balance of workability during molding, curability, and properties of cured products, and are actively used in various fields. It is common knowledge that there are.

In particular, when FRP is combined with reinforcing materials such as glass fiber, it has excellent strength, corrosion resistance, insulation, etc., and is rust-resistant, making it suitable for use in radar domes, tanks, pipes, ducts, weirs, and insulating boards.

Widely used for cable pipes, etc. However, because it is an organic material, it has extremely low resistance to combustion, and as the demand for flame retardant properties has grown stronger recently from the standpoint of safety, there is a tendency for its use to be restricted. do not have. Therefore, many attempts have been made to improve the H flammability of the resin by introducing halogen atoms into the resin skeleton or adding various flame retardants, but at present, sufficient flame retardance has not been achieved. For example, when trying to impart corrosion resistance.

This causes a decrease in other properties such as heat resistance and insulation, and is not necessarily satisfactory.

[Purpose of the invention]

In view of these circumstances, the present invention has been developed without reducing the above characteristics! The object of the present invention is to provide a resin composition that exhibits 1f flammability.

[Disclosure of the invention]

As a result of intensive research to achieve the above object, the inventors have found that by using a specific resin composition, it is possible to create a resin composition that has N1tfA properties, corrosion resistance, heat resistance, insulation, etc. He completed this invention.

That is, the present invention provides a bromine-containing epoxy poly(meth)acrylate (a) obtained by reacting a bromine-containing epoxy resin with an acid component containing (meth)acrylic acid as a main component, which has the following general formula (Δ). An alcohol component (A) containing at least 50 mol% of the compound (1) shown above, and an acid component (A) containing at least 50 mol% of an α,β-unsaturated dicarboxylic acid and/or its anhydride (II). (b) unsaturated polyester obtained by reacting with (b)
b), a polymerizable unsaturated monomer (C), and a flame retardant additive (d) used if necessary, (a), (b),
(c) and (d) are each 100 parts by weight, 20 to 1
The proportions are 20 parts by weight, 30-150 parts by weight and 0-50 parts by weight, and the total bromine content is 15-30% by weight, of which 8-16% by weight is bromine-containing epoxy poly(meth)acrylate ( The gist of the present invention is a resin composition characterized by being based on a).

1-1 General formula (A) Here, the bromine-containing epoxy resin is an epoxy resin having at least one epoxy group in one molecule and having a bromine content of at least 15% by weight, preferably 35% by weight or more. refers to Examples of such bromine-containing epoxy resins include tetrafrom bisphenol A1 tetrabromo bisphenol F1 brominated novolac resin, I,
There is an epoxy resin obtained by polycondensation of a bromine-containing polyhydric phenol such as 1,3-tris(3,5-dibromo-4-hydroxyphenyl)propane and epichlorohydrin. Furthermore, commercially available epoxy resins can be effectively used as these bromine-containing epoxy resins, such as Noepicon 152,1 manufactured by Dainippon Ink Chemical Co., Ltd.
120.153-60M Epicor 1-DX-248-B-8'0. manufactured by Nisiel Chemical Co., Ltd. DX-245:
Sumiepoxy ES+, -3 manufactured by Sumitomo Chemical Co., Ltd.
40°ESB-400, ESB7500. ESB-70
0, ESB-715, etc.

Among bromine-containing epoxy resins, the epoxy equivalent is 60
It is particularly preferable to use 0 or less because the physical properties of a laminate made from the resin composite acid of the present invention will vary widely.

Brome-containing epoxy poly (meth)acrylate (a)
is obtained by reacting a bromine-containing epoxy resin with an acid component whose main component is (meth)acrylic acid.

At this time, the ratio of the epoxy resin and acid component used is one carboxyl group per epoxy group (if the acid component contains an acid anhydride group, one acid anhydride group is considered to be two carboxyl groups).

) 0.7 to 1.5. The acid component contains at least 60 mol % (meth)acrylic acid, and optionally other carboxylic acids and/or carboxylic acid anhydrides. Preferred examples of these carboxylic acids and carboxylic acid anhydrides include phthalic acid, maleic acid, fumaric acid, succinic acid, adipic acid, bromophthalic acid, chlorophthalic acid, Hett's acid, tetrahydrophthalic acid, and 3,6-nindomethylenetetrahydrophthalic acid. acids, acetic acid, propionic acid, dibromopropionic acid, benzoic acid, brobenzoic acid, chlorobenzoic acid, or acid anhydrides thereof.

The bromine-containing epoxy resin and the acid component containing (meth)acrylic acid as a main component can be reacted in various ways. The most common method is to react the epoxy resin and the acid component with a catalyst such as triethylamine, trimethylbenzylammonium chloride, lithium chloride, etc., a stabilizer such as hydroquinone, catechol, picric acid, molecular oxygen, etc., and the necessary This is a method in which the reaction is carried out in the presence of a solvent such as toluene, styrene, or ethyl acetate at a temperature range of 70 to 150°C. At this time, the method of using styrene as a solvent is the reaction product of bromine-containing epoxy poly (
This is a particularly preferred method since it is not necessary to remove the solvent when using meth)acrylate (a).

The unsaturated polyester (b) is an alcohol component (alcohol component) containing at least 50 mol% of the compound (1) represented by the above general formula (Δ) and an α,β-unsaturated dicarboxylic acid and/or its anhydride ( It is a reaction product with an acid component (b) containing at least 50 mol% of hydrogen, and its molecular weight is generally preferably in the range of 500 to 10,000.

If the amount of compound (I), α,β-unsaturated dicarboxylic acid and/or its anhydride ('II) used is out of the above range, heat resistance and corrosion resistance will decrease, making it impossible to achieve the object of this invention. It is not possible and not desirable.

Examples of the α,β-unsaturated dicarboxylic acid and/or its anhydride (II) include maleic anhydride, fumaric acid, itaconic acid, and citraconic acid.

Compounds other than compound (1) used as alcohol component (a) and α, β- used as acid component (b)
Unsaturated dicarboxylic acids and/or their anhydrides (IN)
), as the external compound, any compound known in the unsaturated polyester resin industry can be arbitrarily selected and used. Eiichi Takiyama, "Polyester Resin", page 25, Table 2, 1 (a), and the acids listed in page 26, Table 2, 1
(b) alcohols etc.]

Unsaturated polyester (b) can be produced according to methods known in the art. For example, the alcohol component (a) and acid component (b) selected as above are combined into one
This is a method in which dehydration condensation is carried out in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas in the presence or absence of a catalyst at a temperature range of 50 to 250°C.

The polymerizable unsaturated monomer (C) refers to a compound that is liquid at room temperature and has at least one vinyl unsaturated group in one molecule, such as styrene, vinyltoluene, divinylhensen, α-methylstyrene, etc. , Aromatic vinyl compounds such as chlorostyrene: Vinyl acetate, vinyl esters such as divinyl adipate, etc. Diaryl phthalate: Methyl (meth)acrylate, ethyl (meth)acrylate, octyl (meth)acrylate, di(meth)acrylate Examples include (meth)acrylic esters such as looxyethyl, and one or more of these compounds can be used.

Among these, styrene is particularly preferred because of its solvent performance, polymerization reactivity, and the like.

In carrying out this invention, a flame retardant additive (d) can be used if necessary. Various known flame retardant additives can be used as the flame retardant additive (d), typical examples of which include hexabromocyclododecane, hexabromohenzene, polybrominated biphenyl ether, heptabromo Toluene, 2,2-bisC4-(2,3
dibromopropoxy)3,5-dibromophenyl]propane, 2,4.6-tribromophenol (meth)acrylate, 2,4.6-1-ribromophenol glycidyl ether, brominated epoxy resin as described above, Halogen flame retardants such as tetrachlorophthalic acid, tetrachlorophthalic acid, het acid, perchloropentacyclodecane, etc. Nitrimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate Phate, tricresyl phosphate,
Talesyl phenyl phosphate, octyldiphenyl phosphate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(chloropropyl) phosphate, bis(2,3-
Phosphate esters such as (dibromopropyl) 2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, bis (chloropropyl) octyl phosphate, triallyl phosphate:
Antimony trioxide, etc. Among these, aromatic halogen compounds and aromatic phosphorus compounds that are soluble in resin liquids consisting of brome-containing epoxy poly(meth)acrylate (a), unsaturated polyester (b), and polymerizable unsaturated polymer (C) are used. Acid esters, radically polymerizable halogen compounds, and radically polymerizable phosphoric acid esters are particularly preferable because the resin composition derived therefrom has a good balance of flame retardancy, heat resistance, water resistance, etc.

The resin composition according to the present invention contains 20 to 120 parts by weight of an unsaturated polyester (b) per 100 parts by weight of a bromine-containing epoxy poly(meth)acrylate), and 30 parts by weight of a polymerizable unsaturated monomer (C). ~150 parts by weight, and optionally 0 to 50 parts by weight of a flame retardant additive (d), the total bromine content being 15 to 30% by weight, of which 8 to 16% by weight is bromine. Contains epoxy (meth)
It is based on acrylate (a). (a)-(d
) If the blending ratio of each component and the bromine content are out of the above range, the resulting balance of the physical properties of the resin composition will be disrupted, resulting in a resin composition with good desired physical properties. impossible and undesirable.

The resin composition according to the present invention can be cured in the same manner as the unsaturated polyester resin of lightning, and curing means known in the unsaturated polyester resin industry can be used as is. For example, a method of heating in the presence of a curing agent such as an organic peroxide or a diazo compound, a method of blending an organic peroxide with an accelerator such as a metal soap or an amine compound, and a method of infrared rays in the presence of a photosensitizer. The following can be cured by irradiating electromagnetic waves such as ultraviolet rays and electron beams.
This invention will be further explained by giving an example. In addition,
In the examples, "part j" generally means 1 part by weight.

(Reference Example 1) Epicron 153 was added to a four-eye flask equipped with a thermometer, stirrer, temperature controller, gas inlet tube, and condenser.
(Dainippon Ink & Chemicals Co., Ltd., brominated epoxy resin, epoxy equivalent: 395, bromine content: 49.1% by weight) 895 parts, 0.1 part of hydroquinone, 2.0 parts of triethylamine, 200 parts of styrene, and 72 parts of acrylic acid.
90~100'c while introducing air.
70% by weight of bromine-containing epoxyfoliacrylate with an acid value of 4.2 and ST 12
A resin liquid consisting of 30% by weight (hereinafter referred to as resin (1)).

) was obtained.

(Reference Example 2) The same procedure as in Reference Example 1 was carried out except that 86 parts of methacrylic acid was used instead of 72 parts of acrylic acid, and 206 parts of styrene was used instead of 200 parts of styrene. A resin liquid (hereinafter referred to as resin (2)) consisting of 70% by weight of bromine-containing epoxy polymethacrylate of No. 8 and 30% by weight of styrene was obtained.

(Reference Example 3) A reaction product of 1 mol of bisphenol A and 2.1 mol of propylene oxide (residual phenolic hydroxyl group concentration 120 ppm
, alcoholic hydroxyl group concentration 5.7 equivalents/kg) (hereinafter referred to as BPA72.IPO) and 98 parts of maleic anhydride were added, and the acid value was 3 at 200°C under a nitrogen stream.
8, and polyester (1) is iM.

(Reference Example 4) In the same manner as in Reference Example 3, except that 245 parts of BPA-2, IPO and 36 parts of neopentyl glycol were used instead of 360 parts of BPA-2, IPO, an acid value of 33 of polyester (2) was obtained.

(Reference Example 5) 111 parts of diethylene glycol, 66,4 parts of isophthalic acid
An unsaturated polyester having an acid value of -21 (hereinafter referred to as polyester (3)) 217 was prepared in the same manner as in Reference Example 3 using 29.2 parts of adipic acid and 46.4 parts of fumaric acid.
I got the department.

(Example 1) The following resin composition Resin (1) 100 parts Polyester (1) 50 parts Styrene 20 parts Hensyl baroxide 1.7 parts Antimony dioxide 2 parts were mixed with glass cloth WE-18K manufactured by Nittobo Co., Ltd. -B.S.
) and stack 8 sheets of this impregnated glass cloth,
Further, electrolytic copper foils having a thickness of 18 μm were stacked on both sides of the foil, passed between rolls having a clearance of 1.60 mm, and then cured at 90° C. for 15 minutes and then at 120° C. for 1 hour. The thickness of the obtained copper-clad laminate was approximately 1.6 mm.

(Example 2) The following resin composition resin (1110 (1 part polyester (2) 50 parts diallyl phthalate 40 parts Hensil peroxide 1.9 parts tricresyl phosphate 2 parts) was mixed with glass cloth (Nittobo Co., Ltd. Made by WE-18-BS
), placed on an electrolytic copper foil having a thickness of 35 μm, and then impregnated with a resin composition on top of the glass nonwoven fabric (Ep-405ONV, manufactured by Nippon Vilene Co., Ltd.)
Three sheets were stacked, and the above glass cloth impregnated with the resin composition was stacked, and an electrolytic copper foil having a thickness of 35 μm was stacked on top of the glass cloth, and then a clearance of 1.65+n+n was stacked.
After passing between the rolls set at 100℃ and 60℃
The molding was carried out under heat and pressure conditions of 10 kg/cJ for 1 minute to obtain a copper-clad laminate having a thickness of 1°6 mm.

(Example 3) The following resin composition resin (21,100 parts polyester (1,150 parts styrene, 30 parts benzoyl peroxide, 1.8 parts tricresyl phosphate, 2 parts, 1 part) was mixed with the same glass as that used in Example 1. Impregnated cloth, stacked 8 sheets of impregnated glass cloth, and added 1 layer of thick cloth to both sides.
After stacking 8μm electric M copper foils and passing them between rolls with a clearance of 1.60mm, they were heated at 90°C for 3
It was molded under heating and pressure conditions of 5 kg/ctA for 0 minutes, and then heated at 150° C. for 15 minutes to form a copper-clad laminate with a thickness of 1.5 mm.

(Example 4) The following resin composition Resin (2) 100 parts; Polyester + 21 40 parts Styrene 20 parts Hensyl peroxide 1.6 parts Antimony trioxide 2 parts was added to the same glass as that used in Example 1. The fabric was impregnated and placed on a polyester film (Lumirror, manufactured by Toshi Co., Ltd.) with a thickness of 100 μm, and then the same glass nonwoven fabric used in Example 2 was impregnated with the resin composition. The sheets were stacked together, and the glass cloth impregnated with the resin composition was further stacked thereon. Next, after passing between the rolls with a clearance of 70 mm,
It was cured at 110°C for 10 minutes and then at 130°C for 1 hour, and the polyester film on one side was cured with rAl 41.
A copper-clad laminate having a thickness of 1.6 mm was obtained.

(Comparative Example 1) The same glass cloth used in Example 1 was impregnated with the following resin composition Resin+11 100 parts polyester (3150 parts styrene 20 parts benzoyl peroxide 1.7 parts antimony trioxide 2 parts),
A copper-clad laminate was obtained in the same manner as in Example 1. The thickness was approximately 1.6 mm.

Table 1 shows the characteristics evaluation results of these Examples and Comparative Examples.

(Margin below) 1) Weight (W+) after removing the copper foil and heating a test piece cut into 50 mm x 50 mm at 100°C for 30 minutes
Measure the temperature and then heat it to 133℃ with a pressure cutter 9
After treatment for 0 minutes, the test piece was left in a room adjusted to 60R,1% at 20°C, and after the specimen cooled to room temperature, its weight
(W2) is measured, and the water absorption rate is calculated using the following formula.

1 2) After measuring the weight (W2), the test piece is immersed in a solder bath at 260°C, and the time until blistering occurs is measured.

3) The test was conducted according to JISC-6481. The numbers in parentheses indicate the pretreatment conditions for the test piece.

(Example 5) Resin (21,100 parts, polyester (1,130 parts).

Cobalt octenoate (metal content: 8% by weight) is added to a resin solution containing 20 parts of styrene and 8 parts of antimony trioxide.
) and 2 parts of methyl ethyl ketone peroxide (peroxide content: 55% by weight) were injected between parallel glass plates and cured to create a flat plate.The physical properties were measured.The results are as follows. be.

Bending strength 13.7 kg/mm Bending modulus 430 Tensile strength 8.1 Tensile elongation 3.7% Heat distortion temperature 127 ℃ Combustion test oxygen index 45 Water resistance (100 ℃) No change in appearance after 100OH Insulation resistance State: 3X1014 Ω After boiling in water for 2 hours: 1X1013 Ω [Effects of the Invention] The resin composition according to the present invention is flame retardant, and has excellent corrosion resistance, heat resistance, insulation, etc., so it is effective in various uses. It can be used for. In particular, flame retardancy, corrosion resistance, and heat resistance are effective in tanks, pipes, ducts, etc., and cable pipes, switch boxes,
Since flame retardancy, corrosion resistance, heat resistance and insulation properties are extremely effective in insulating plates and the like, these are particularly preferred forms of use.

Agent: Patent Attorney Takehiko Matsumoto

Claims (1)

[Scope of Claims] (11 Brome-containing epoxy poly (meth)acrylate (a) obtained by reacting a brome-containing epoxy resin with an acid component containing (meth)acrylic acid as a main component, the following general formula (A) ) An alcohol component (A) containing at least 50 mol% of the compound (■) represented by ) and at least 50 mol% of α,β-unsaturated dinorphonic acid/or its anhydride (II) Consisting of an unsaturated polyester (b) obtained by reacting with an acid component (b), a polymerizable unsaturated monomer (C), and a flame retardant additive (, d) used as necessary, (a), (b), (c) and (
d) is 100 parts by weight, 20 to 120 parts by weight, and 3 parts by weight, respectively.
The ratio is 0 to 150 parts by weight and 0 to 50 parts by weight,
The total bromine content is 15 to 30% by weight, and 8
A resin composition characterized in that ~16% by weight is based on bromine-containing epoxy poly(meth)acrylate (a).