JPS6225685B2 - - Google Patents

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 radically polymerizable thermosetting resins such as unsaturated polyester resins, have a good balance in workability during molding, curability, and properties of cured products, and are active in various fields. As is widely known, it is used for In particular, when combined with reinforcing materials such as glass fiber to make FRP, it has excellent strength, corrosion resistance, and insulation properties, and because it does not rust, it is widely used in radar doors, tanks, pipes, ducts, weirs, insulating plates, cable pipes, etc. It is widely used. However, because it is organic, it has extremely low resistance to combustion, and as the demand for flame retardancy has grown stronger recently, its use has tended to be restricted from the standpoint of safety. I can't deny it. Therefore, many attempts have been made to improve the flame retardancy of the resin by introducing halogen atoms into the resin skeleton or adding various flame retardants, but at present, sufficient flame retardancy has not been achieved. If an attempt is made to impart such properties, for example, other properties such as corrosion resistance, heat resistance, and insulation properties may deteriorate, which is not necessarily satisfactory. [Object of the Invention] In view of the above circumstances, an object of the present invention is to provide a resin composition that can be imparted with flame retardancy without reducing the above-mentioned properties. [Disclosure of the Invention] As a result of intensive research to achieve the above object, the inventors have developed a resin composition that has flame retardancy, corrosion resistance, heat resistance, insulation, etc. by using a specific resin composition. He made this possible and 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, and having the following general formula (A). An alcohol component (a) containing at least 50 mol% of the compound () shown above and at least an α,β-unsaturated dicarboxylic acid and/or its anhydride ().
An unsaturated polyester (b) obtained by reacting an acid component (b) containing 50 mol%, a polymerizable unsaturated monomer (c), and a flame retardant additive (d) used as necessary.
(a), (b), (c) and (d) are respectively 100 parts by weight, 20-120 parts by weight, 30-150 parts by weight and 0-150 parts by weight.
50 parts by weight ratio, total bromine content 15-30
The gist of the resin composition is that 8 to 16% by weight of the resin composition is based on bromine-containing epoxy poly(meth)acrylate (a). General formula (A) [However, m and n are each independently an integer of 1 to 4 and satisfy the formula 2≦n+m≦5,
R ₁ and R ₂ are each independently an alkylene group having 2 to 3 carbon atoms, and may be different for each repeating unit shown in parentheses. ] Here, the bromine-containing epoxy resin has at least one epoxy group in one molecule, and the brome content is at least 15% by weight, preferably 35% by weight.
Refers to epoxy resins that are the above. Examples of such bromine-containing epoxy resins include tetrabromobisphenol A, tetrabromobisphenol F, brominated novolac resins, 1,1,3-tris(3,5-dibromo-4-hydroxyphenyl) There is an epoxy resin obtained by polycondensation of a bromine-containing polyphenol such as propane and epichlorohydrin. In addition, commercially available epoxy resins can be effectively used as these bromine-containing epoxy resins, such as Epiclon 152, 1120, 153-60M manufactured by Dainippon Ink and Chemicals Co., Ltd.; Epicort DX manufactured by Ciel Chemical Industry Co., Ltd. -248-B-
80, DX-245: Sumiepoxy ESB-340, ESB-400, ESB-500, ESB manufactured by Sumitomo Chemical Co., Ltd.
-700, ESB-715, etc. Among the bromine-containing epoxy resins, those having an epoxy equivalent of 600 or less are particularly preferred because they provide a good balance of physical properties when the resin composition of the present invention is used as a laminate. 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
~1.5 pieces. 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, bromphthalic acid, chlorphthalic acid, hectic acid, tetrahydrophthalic acid, 3,6-endomethylenetetrahydrophthalic acid, acetic acid, propionic acid, dibromopropionic acid, benzoic acid, bromobenzoic acid, chlorbenzoic acid Acids or their acid anhydrides. 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 among these 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. In this case, the method of using styrene as a solvent is a particularly preferred method since it is not necessary to remove the solvent when using the bromine-containing epoxy poly(meth)acrylate (a) as a reaction product. The unsaturated polyester (b) consists of an alcohol component (a) containing at least 50 mol% of the compound () represented by the above general formula (A), and an α,β-unsaturated dicarboxylic acid and/or its anhydride ( ) is a reaction product with an acid component (b) containing at least 50 mol % of the acid component (b), and its molecular weight is usually preferably in the range of 500 to 10,000. If the amount of the compound () or α,β-unsaturated dicarboxylic acid and/or its anhydride () used is outside the above range, heat resistance and corrosion resistance will decrease, making it impossible to achieve the objectives of the present invention. I can't do it and I don't like it. Examples of the α,β-unsaturated dicarboxylic acid and/or its anhydride include maleic anhydride, fumaric acid, itaconic acid, and citraconic acid. Compounds other than the compound () used as the alcohol component (a) and compounds other than the α,β-unsaturated dicarboxylic acid and/or its anhydride () used as the acid component (b) include unsaturated polyester resins. Those known in the industry can be arbitrarily selected and used [for example, "Polyester Resin" by Eiichiro Takiyama, published by Nikkan Kogyo Shimbun (August 30, 1980, 9th edition), page 25, Table 2・Acids listed in 1(a) and alcohols listed in Table 2.1(b) on page 26 of the same). Unsaturated polyester (b) can be produced according to methods known in the art. For example, alcohol component (a) and acid component selected as above
This is a method in which (b) is subjected to dehydration condensation in a temperature range of 150 to 250°C in the presence or absence of a catalyst in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas. 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, divinylbenzene, α-methylstyrene, etc. ,
Aromatic vinyl compounds such as chlorostyrene: Vinyl acetate, vinyl esters such as divinyl adipate: Diallyl phthalate: Methyl (meth)acrylate, octyl (meth)acrylate, octyl (meth)acrylate, di(meth)acrylate
Examples include (meth)acrylic esters such as acryloxyethyl, 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. Flame retardant additive (d)
Various known flame retardant additives can be used as the flame retardant additive, and representative examples include hexabromocyclododecane, hexabromobenzene, polybrominated biphenyl ether, heptabromotoluene, 2,2-bis [4-(2,3-dibromopropoxy)3,5-dibromophenyl]propane,
2,4,6-tribromophenol (meth)arylate, 2,4,6-tribromophenol glycidyl ether, brominated epoxy resin as mentioned above, tetrabromophthalic acid, tetrachlorofuric acid, hettic acid, perchloropenta Halogen flame retardants such as cyclodecane: trimethyl phosphate,
Triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, Tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) 2,3-
Dichloropropyl phosphate, Tris(2,
Phosphate esters such as 3-dibromopropyl) phosphate, bis(chloropropyl)octyl phosphate, and triallylphosphate:
Antimony trioxide, etc. Among these, aromatic halogen compounds and aromatic phosphorus compounds that are soluble in resin liquids made of bromine-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 unsaturated polyester (b) and 30 to 150 parts by weight of polymerizable unsaturated monomer (c) per 100 parts by weight of bromine-containing epoxy poly(meth)acrylate (a). parts by weight and, if necessary, a flame retardant additive (d). It is based on meth)acrylate(a). (a)
If the blending ratio of each component in ~(d) and the bromine content are out of the above range, the resulting balance of physical properties of the resin composition will be lost, and the resin composition will not have the desired physical properties. Unobtainable and undesirable. The resin composition according to the present invention can be cured in the same manner as ordinary unsaturated polyester resins, 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, a method of heating in the presence of a photosensitive agent, It can be cured by a method of irradiating electromagnetic waves such as ultraviolet rays and electron beams. Hereinafter, the present invention will be explained in more detail by giving examples. In addition, "parts" in the examples generally indicate "parts by weight." (Reference Example 1) Epiclon 153 (manufactured by Dainippon Ink & Chemicals Co., Ltd., brominated epoxy resin, epoxy equivalent: 395,
Bromine content 49.1% by weight) 395 parts, hydroquinone 0.1 part, triethyleneamine 2.0 parts, styrene
200 parts of acrylic acid and 72 parts of acrylic acid were charged and reacted for 11 hours at a temperature range of 90 to 100°C while introducing air to obtain a resin liquid (by weight) consisting of 70% by weight of bromine-containing epoxy polyacrylate with an acid value of 4.2 and 30% by weight of styrene. (hereinafter referred to as resin (1)) was obtained. (Reference Example 2) The same procedure was used as in Reference Example 1, 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 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 BPA-2.1PO) and 98 parts of maleic anhydride were added and reacted under a nitrogen stream at 200°C until the acid value reached 38 to obtain polyester (1). . (Reference Example 4) Polyester with an acid value of 33 ( 2) was obtained. (Reference example 5) 111 parts of diethylene glycol, isophthalic acid
An unsaturated polyester with an acid value of 21 (hereinafter referred to as polyester (3)) 217 was prepared in the same manner as in Reference Example 3 using 66.4 parts of adipic acid, 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 Benzoyl peroxide 1.7 parts Antimony trioxide 2 parts was mixed with glass cloth (WE-18K manufactured by Nittobo Co., Ltd.)
BS), and stacked 8 sheets of impregnated glass cloth, and then layered electrolytic copper foil with a thickness of 18 μm on both sides to obtain a clearance of 1.60.
The film was passed between rolls of 1.5 mm in diameter, 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 (1) 100 parts polyester (2) 50 parts diallyl phthalate 40 parts benzoyl peroxide 1.9 parts tricresyl phosphate 2 parts was mixed with glass cloth (Nittobo Co., Ltd. WE). ―18K―
A glass nonwoven fabric impregnated with a resin composition (manufactured by Nippon Vilene Co., Ltd.) was placed on an electrolytic copper foil with a thickness of 35 μm.
Ep-4050NV) are stacked together, the above-mentioned glass cloth impregnated with the resin composition is stacked, and an electrolytic copper foil with a thickness of 35 μm is stacked on top of that, and then between the rolls with a clearance of 1.65 mm, After passing through, a copper clad laminate with a thickness of 1.6 mm was formed by heating and pressing at 10 kg/cm ² at 100° C. for 60 minutes. (Example 3) The following resin composition Resin (2) 100 parts Polyester (1) 50 parts Styrene 30 parts Benzoyl peroxide 1.8 parts Tricresyl phosphate 2 parts were added to the same glass as used in Example 1. A cloth was impregnated, 8 sheets of the impregnated glass cloth were layered, and electrolytic copper foil with a thickness of 18 μm was layered on both sides of the cloth, passed between rolls with a clearance of 1.60 mm, and then heated at 90℃ for 30 minutes. The molding was carried out under heat and pressure conditions of 5 kg/cm ² for 1 minute, and then heated at 150° C. for 15 minutes to obtain a copper-clad laminate having a thickness of 1.6 mm. (Example 4) The same glass cloth used in Example 1 was impregnated with the following resin composition Resin (2) 100 parts Polyester (2) 40 parts Styrene 20 parts Benzoyl peroxide 1.6 parts Antimony trioxide 2 parts Then, it was placed on a polyester film (Lumirror, manufactured by Toray Industries, Inc.) with a thickness of 100 μm, and then two sheets of the same glass nonwoven fabric impregnated with a resin composition as used in Example 2 were superimposed on this. Furthermore, the above-mentioned glass cloth impregnated with the resin composition was laminated on top of each other. Next, after layering electrolytic copper foil with a thickness of 35 μm, it was passed between rolls with a clearance of 1.70 mm, and then heated at 110°C for 10 minutes.
It was further cured at 130° C. for 1 hour, and the polyester film on one side was peeled off to obtain a copper-clad laminate with a thickness of 1.6 mm. (Comparative Example 1) The same glass cloth used in Example 1 was impregnated with the following resin composition Resin (1) 100 parts Polyester (3) 50 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.

【table】

〔Effect of the invention〕

The resin composition according to the present invention is flame retardant and has excellent corrosion resistance, heat resistance, insulation properties, etc., and therefore can be effectively used in various applications. In particular, flame retardancy, corrosion resistance, and heat resistance are effective for tanks, pipes, ducts, etc.
Cable pipes, switchboxes, insulating plates, etc. have particularly effective flame retardancy, corrosion resistance, heat resistance, insulation properties, etc., and are therefore particularly preferred forms of use.

Claims (1)

[Claims] 1. Brome-containing epoxy poly(meth)acrylate obtained by reacting a bromine-containing epoxy resin with an acid component containing (meth)acrylic acid as a main component.
(a), an alcohol component (a) containing at least 50 mol% of the compound () represented by the following general formula (A);
and an acid component (b) containing at least 50 mol% of α,β-unsaturated dicarboxylic acid and/or its anhydride (b), a polymerizable unsaturated monomer (a), (b),
(c) and (d) are in proportions of 100 parts by weight, 20 to 120 parts by weight, 30 to 150 parts by weight, and 0 to 50 parts by weight, respectively, and the total bromine content is 15 to 30 parts by weight, and A resin composition characterized in that 8 to 16% by weight is based on bromine-containing epoxy poly(meth)acrylate (a). -Note- General formula (A) [However, m and n are each independently an integer of 1 to 4 and satisfy the formula 2≦n+m≦5, and R ₁ and R ₂ are each independently an alkylene group having 2 to 3 carbon atoms. and may be different for each repeating unit indicated in parentheses. ]