JPH02279752A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition improved in heat resistance, impact resistance and flame retardancy by mixing a heat-resistant resin with a thermo plastic resin, Sb2O3, a specified reaction product and a functional alkoxysilane. CONSTITUTION:100 pts.wt. mixture of a heat-resistant resin (A) which is a copolymer of a styrene compound with an imide compound of alpha,beta-unsaturated dicarboxylic acid and may be reinforced with a rubber reinforcement with a thermoplastic resin (B) selected from an impact-resistant resin prepared by grafting styrene and acrylonitrile or methyl acrylate onto a butadiene rubber, an ethylene/propylene rubber or an acrylate rubber, and a copolymer resin of styrene with acrylonitrile or methyl methacrylate is mixed with 0.5 to 10 pts.wt. Sb2O3 (C), 5.0 to 40 pts.wt. reaction product of a brominated epoxy compound (D) of an epoxy equivalent of 450 to 7000 and a Br content of 5.0 to 52wt.% with an acrylonitrile/butadiene copolymer having a mol.wt. of 1000 to 10000 and having carboxyls on both ends and 0.1 to 3.0 pts.wt. functional alkoxysilane (E) selected from among a mercaptoalkoxysilane, a methacryloylalkoxysilane and a vinyltrialkoxysilane.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a resin composition having excellent heat resistance. More specifically, it not only has excellent heat resistance, but also
The present invention relates to a resin composition that has good impact resistance and excellent flame retardancy and is promising as a material for parts of electronic devices, electrical devices, and the like.

[Prior art] Currently, flame-retardant acrylonitrile-butadiene-styrene ternary copolymer resin (ABS resin) is used as housings for electronic and electrical equipment such as television sets, CRTs, various computers, facsimiles, and word processors. Styrenic resins are commonly used. In addition, there are polyphenylene oxide resins (PPO) and polycarbonate resins (PC) as synthetic resins that have a heat resistance temperature of 100°C or higher, but they have problems in moldability, are cheap, and have heat resistance and flame retardancy. There is a need for synthetic resins or compositions thereof that have excellent properties. Furthermore, in order to improve the moldability of PPO and PC, it has been proposed to blend heat-resistant resins such as styrene-maleimide polymers into these synthetic resins (
(U.S. Pat. No. 4,278,775, U.S. Pat. No. 4,160,792)
. These compositions have good heat resistance and moldability, but
There are problems with flame retardancy. Furthermore, it has been proposed to blend a styrene-maleimide polymer into a vinyl chloride resin (US Pat. No. 4,458,046). Furthermore, it has been proposed to add a halogen flame retardant such as decadibromodiphenyl ether to a styrene-maleimide polymer (Japanese Patent Laid-Open No. 82950/1983). Furthermore, along with monomers such as styrene compounds and maleimide compounds, brominated phenylmaleimide compounds (
Attempts have also been made to copolymerize with halogen-containing monomers such as JP-A-61-157511) and brominated (meth)acrylate compounds (JP-A-52-82990). [Problem to be solved by the invention l However, the heat resistance temperature (measured according to ASTM D648, 18.5 kg/Cd) of the above-mentioned flame-retardant styrene resin such as ABS resin is usually 70 to 90°C.
However, depending on the use and size of the product, problems often arise regarding heat resistance. Furthermore, compositions in which PPO or PC is blended with a heat-resistant resin such as a styrene-maleimide polymer have good heat resistance and moldability, but have problems in terms of flame retardancy. Furthermore, although compositions made of vinyl chloride resin and styrene-maleimide polymers have excellent flame retardancy, they have problems with heat resistance. Compositions to which a flame agent is added tend to cause dripping and have problems with flame retardancy. In addition, brominated phenylmaleimide compounds, as well as styrene compound and maleimide compound monomers,
Multi-component copolymers obtained by copolymerizing halogen-containing monomers such as brominated (meth)acrylate compounds require a large amount of expensive halogen-containing monomers to provide sufficient flame retardancy. This poses a practical problem. For these reasons, it not only has excellent flame retardancy, but also
There is a demand for synthetic resins or compositions thereof that have good heat resistance and impact resistance as well as excellent moldability. From the above, the present invention does not have these drawbacks (problems) (i.e., it not only has excellent heat resistance and impact resistance, but also has good flame retardancy and moldability, and is relatively inexpensive. [Means and effects for solving the problems] According to the present invention, 1. These problems are as follows: and (2) a copolymer of a styrene compound reinforced with a rubber reinforcing material and an imide compound of α,β-unsaturated dicarboxylic acid. (Bl Impact-resistant resin obtained by graft copolymerizing styrene and acrylonitrile or styrene and methyl methacrylate to butadiene rubber, ethylene-propylene rubber or acrylic ester rubber, and styrene and acrylonitrile or styrene) at least one thermoplastic resin selected from the group consisting of a copolymer resin of tc) and methyl methacrylate; tc) antimony oxide;
and a bromine-containing epoxy compound having a bromine content of 5.0 to 52% by weight, a carboxyl group at both ends, and a molecular weight of 1,000 to 10%. [) Reaction product with acrylonitrile-butadiene copolymer which is DO and fE) At least one functional group-containing alkoxysilane selected from the group consisting of mercapto group-containing alkoxysilane, methacryloyl group-containing alkoxysilane and vinyltrialkoxysilane. The proportions of the styrene compound and imide compound, which are copolymerized components of the heat resistant resin, in the total amount of the heat resistant resin and thermoplastic resin are 10 to 50% by weight, respectively, and The proportion of imide compounds in the total amount of compounds and imide compounds is 5
~50% by weight, and the proportions of rubber reinforcing materials used in the production of heat-resistant resins and butadiene rubber, ethylene-propylene rubber, and acrylic ester rubber used in the production of impact-resistant resins are the sum of these. 5~ as quantity
The amount of antimony oxide is 35% by weight, and the amount of antimony oxide is 0.5 to I
0 parts by weight, the reaction product is 5.0 to 4Q parts by weight, and the functional group-containing alkoxysilane is 0.1 to 3.0 parts by weight.
parts by weight of the resin composition. Hereinafter, five aspects of the present invention will be explained in detail. fA+ 1t heat-resistant resin The heat-resistant resin used in the present invention is selected from the following. (11) Copolymer of at least a styrene compound and an imide compound of α,β-unsaturated dicarboxylic acid (hereinafter referred to as “heat-resistant resin (1)”) (2) At least a styrene compound reinforced with a rubber reinforcing material A copolymer of a compound and an imide compound of α,β-unsaturated dicarboxylic acid (hereinafter referred to as “heat-resistant resin (2)”) Even in the case of the above heat-resistant resin fl), heat-resistant resin (2)
In this case, the styrene compound which is a copolymerization component is styrene or its derivatives, and the derivatives include α-methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, and chlorostyrene. It will be done. Further, examples of imide compounds of α,β-unsaturated dicarboxylic acids include those whose -killing properties are represented by formula (1). In formula (I), R, T(2 and R1 may be the same or different, and are a hydrogen atom and a hydrocarbon group having at most 12 carbon atoms. As a representative example of the imide compound, 71/imide , N
-phenylmaleimide, N-methylphenylmaleimide, N-ethylphenylmaleimide, N-laurylmaleimide, and the like. Further, in producing the heat-resistant resin (2), rubber reinforcing materials used as reinforcing materials include styrene-butadiene copolymer rubber (styrene copolymerization ratio is usually 40% by weight or less), butadiene homopolymer rubber, Styrene
Examples include hydrogenated styrene-butadiene copolymer rubber obtained by hydrogenating butadiene copolymer rubber and copolymer rubber of ethylene and propylene. The heat-resistant resin (2) is obtained by graft polymerizing a styrene compound and the imide compound to a rubber reinforcing material, and the ratio of rubber reinforcing material used is usually 3 parts per 121,100 parts by weight of the heat-resistant resin. ~20 parts by weight (preferably 5 to 15 parts by weight). In the case of heat-resistant resin +1) and heat-resistant resin (2), the commonly used aqueous suspension polymerization method,
It can be produced by any one of emulsion polymerization, solution polymerization, and bulk polymerization, and the methods for producing these heat-resistant resins are well known. In addition, in the case of any heat-resistant resin, the copolymerization ratio of the imide compound in the total amount of the styrene compound and the imide compound of α,β-unsaturated dicarboxylic acid, which are copolymerization components, is 5 to 5. 50% by weight, 10-50% by weight
is desirable, particularly 10 to 45% by weight. If the copolymerization ratio of the imide compound to the total amount of the styrene compound and the imide compound is less than 5% by weight, heat resistance will be insufficient. On the other hand, when it exceeds 50% by weight, moldability is significantly reduced. In addition, in the case of any heat-resistant resin, it may be composed of a styrene compound and an imide compound as copolymerization components, but it is also possible to copolymerize an unsaturated nitrile monomer such as acrylonitrile and methacrylate or methyl methacrylate. A copolymerized component (copolymerization ratio, usually at most 30% by weight) may also be used. Furthermore, a relatively large amount of rubber reinforcing material may be used as the heat-resistant resin (2) and graft copolymerized, and the resulting graft copolymer may be used as a master batch by blending the heat-resistant resin (11, etc.) Even in the case of the above heat-resistant resin (1), heat-resistant resin (2)
Even in this case, only one type of rubber reinforcing material may be used in producing the styrene compound, imide compound, and heat-resistant resin (2), or two or more types may be used in combination. IBI thermoplastic resin The thermoplastic resin used in the present invention is a rubber selected from the group consisting of butadiene rubber, ethylene-propylene rubber, and acrylic ester rubber, grafted with styrene and acrylonitrile or styrene and methyl methacrylate. It is selected from the group consisting of impact-resistant resins obtained by polymerization and "copolymer resins of styrene and acrylonitrile or styrene and methyl methacrylate" (hereinafter referred to as "styrenic copolymer resins"). +11 Impact-resistant resin The rubber used in the production of the impact-resistant resin in the present invention is selected from butadiene homopolymer rubber and random or block copolymer rubber of butadiene and a small amount (usually 40% by weight or less) of styrene or acrylonitrile. Butadiene rubber, copolymer rubber of ethylene and propylene, and small amounts of ethylene and propylene (generally
10% by weight or less) of two double bonds at the ends (for example, 1.4-
pentagene), linear or branched diolefins containing only one terminal double bond (e.g. l,4-hexadiene) and bicyclo[2,2,13-hebutene-2
or ethylene-propylene rubber selected from multicomponent copolymer rubbers with acrylic esters (e.g., butyl acrylate) or acrylic esters and small amounts (generally 10% by weight or less) and other monomers (e.g., butyl acrylate). , acrylonitrile). In producing the impact-resistant resin of the present invention, among these rubber-like substances, those having a Mooney viscosity of 20 to 140 are preferable, although it varies depending on the type of the rubber-like substance, and those having a Mooney viscosity of 30 to 120 are particularly preferable. It is. Further, these rubber-like materials are widely produced industrially and are used in a wide variety of fields. Their manufacturing methods, properties and uses are widely known.
For example, Shu Kambara, "Synthetic Rubber Handbook" (1961, published by Shokusoku Shoten) 1. In producing the impact-resistant resin of the present invention, graft polymerization methods include bulk polymerization, solution polymerization, emulsion polymerization. There are legal and aqueous suspension polymerization methods as well as methods that combine these graft polymerization methods (for example, bulk polymerization followed by aqueous suspension polymerization). Generally, the amount of rubber material used to produce 100 parts by weight of impact resistant resin is 3 to 40 parts by weight, preferably 5 to 35 parts by weight,
In particular, 5 to 30 parts by weight is suitable (a relatively large amount of the rubbery material is used to produce a graft polymer containing a large amount of the rubbery material, and the graft polymer is added to the above-mentioned styrene, acrylonitrile, methyl Methacrylate homopolymer resin or copolymer resin may be mixed, but in this case, the amount of rubbery material used is calculated as a mixture).Also, the monomer bonded to the rubbery material as a graft chain (styrene , acrylonitrile, methyl methacrylate) is usually from t,ooo to 300,000, preferably from 2,000 to 200,000.In general, it is rare for monomers to be completely bonded to a rubber-like material, and it is difficult to graft There are homopolymers or copolymers of monomers that do not bond to rubber-like materials.These homopolymers and copolymers are used as they are without being separated.The impact-resistant resin produced as described above Typical examples include butadiene homopolymer rubber, block or random copolymer rubber of styrene and butadiene (SBR), or acrylonitrile and butadiene copolymer rubber (NBR),
Acrylonitrile-butadiene-obtained by craft copolymerization of styrene and acrylonitrile
Styrene ternary copolymer resin (ABSf-1 resin), methyl methacrylate-butadiene-styrene ternary copolymer resin (MBS resin) obtained by craft copolymerizing styrene and methyl methacrylate to butadiene homopolymer rubber or SBR, Acrylonitrile-acrylic ester-styrene ternary copolymer resin (AAS resin) obtained by graft copolymerizing acrylonitrile and styrene onto acrylic ester rubber, and graft copolymerizing acrylonitrile and styrene onto ethylene-propylene rubber. Examples include kraft copolymer resins (AES resins) obtained by Furthermore, in the production of the above impact resistant resin, a relatively large amount (generally 40 to 70% by weight) of rubber is graft copolymerized with styrene and acrylonitrile or styrene and methyl methacrylate in the same manner as in the production of the impact resistant resin. Using a high rubber concentration impact resistant resin (for example, a high rubber concentration acrylonitrile-butadiene-styrene ternary copolymer resin) obtained by the method, the heat-resistant resin described above, and the styrenic copolymer resin described later, The composition ratio may be adjusted within a range. These impact-resistant resins are manufactured industrially and are used in a wide variety of fields. Moreover, the manufacturing method is well known. (2) Styrene copolymer resin Furthermore, the styrene copolymer resin used as a thermoplastic resin is a copolymer resin of styrene and acrylonitrile (A
SII resin) and a copolymer resin of styrene and methyl methacrylate (MS resin). The copolymerization ratio of styrene in these styrene-based copolymer resins is generally 40 to 8.
5% by weight (preferably 50 to 80% by weight). This styrene-based copolymer resin is industrially produced by a polymerization method similar to the above-mentioned graft polymerization, and is used in a wide variety of fields. tct Antimony mide Furthermore, the antimony oxide used in the present invention is widely used as a flame retardant aid for general bromine-containing compounds. Typical examples include antimony dioxide, antimony pentoxide, and these antimony oxides. The average particle size of the antimony oxide is 1-150 μm. fD) Reaction products The reaction products also useful in the present invention are: A bromine-containing epoxy compound with an epoxy equivalent of 450 to 7,000 and a bromine content of 5.0 to 52% by weight, a carboxyl group at both ends, and a molecular weight of 1,
It is obtained by reacting with an acrylonitrile-butadiene copolymer of 000 to ooo. The bromine content of the bromine-containing epoxy compound is 5.0 to 5.
2% by weight, preferably from 7.0 to 52% by weight, particularly preferably from 10 to 52% by weight, but is not preferred because it causes a decrease in surface gloss. The general formula of the bromine-containing epoxy compound is represented by the following formula [(■) formula]. The flame retardance of the bromine-containing epoxy compound is not good, and the epoxy equivalent of the bromine-containing epoxy compound is 450 to 7.000.
~6.000 is preferred, especially 500~s, o
oo is preferred. If a bromine-containing epoxy compound with an epoxy equivalent of less than 450 is used, the heat resistance will be poor; on the other hand, if one with an epoxy equivalent of more than 7,000 is used,
Due to poor compatibility, the bromine-containing epoxy compound on the surface of the molded article contains at least one bromine atom,
4”-dioxydiphenylpropane (bisphenol A
) and epichlorohydrin can also be produced in the same manner as general ether type epoxy resins. It can also be produced by reacting bromine-free ether-type epoxy resin with bromine. Further, the molecular weight of the acrylonitrile-butadiene copolymer having carboxyl groups at both ends is 1.000 to 10.
,000, preferably t, soo to s, ooo, and particularly preferably 2.000 to 7.000. When an acrylonitrile-butadiene copolymer having a molecular weight of less than 1,000 is used, there is a problem in the impact resistance of the resulting composition. On the other hand, if an acrylonitrile-butadiene copolymer exceeding to or ooo is used, there is a problem in terms of compatibility with the above-mentioned bromine-containing epoxy compound. Additionally, this compound's acrylonitrile −°
The copolymerization proportion of acrylonitrile in the butadiene copolymer portion is at most 40% by weight. If the copolymerization ratio of acrylonitrile exceeds 40% by weight, the viscosity increases significantly, making handling difficult. The reaction product of the present invention can be obtained by reacting a bromine-containing epoxy compound with an acrylonitrile-butadiene copolymer having carboxyl groups at both ends. Methods for obtaining the reaction product include a method of heating both at high temperatures and a method of heating in the presence or absence of a solvent using an amine catalyst. Any method can be applied to obtain the reaction product of the present invention. The reaction ratio of the acrylonitrile-butadiene copolymer having carboxyl groups at both ends with respect to 100 parts by weight of the bromine-containing epoxy compound is generally 5.0 to 100 parts by weight, particularly preferably 5.0 to 80 parts by weight. If the reaction ratio of the acrylonitrile-butadiene copolymer having carboxyl groups at both ends with respect to 100 parts by weight of the bromine-containing epoxy compound is less than 5.0 parts by weight, the effect of improving impact resistance is not sufficient. On the other hand, if it exceeds 1001ffi parts, there is a problem in terms of heat resistance. IEI functional group-containing alkoxysilane Among the functional group-containing alkoxysilanes used in the present invention, representative examples of mercapto group-containing alkoxysilanes include those represented by the following formula [(■) formula]. fls-R'-5i+OR'), (II[) (In the formula [1), R6, R7 and R'' may be the same or different (, linear or branched alkyl having 1 to 6 carbon atoms) group, and X is 2 or 3. Representative examples of the mercapto group-containing alkoxysilane represented by formula (III) include γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl!-rimethoxysilane, etc. In addition, representative examples of methacryloyl group-containing alkoxysilanes include those shown by the following formula [(■) Formula J. (Left blank below) In formula (1v), R8, R%, and RIG may be the same or different. is a linear or branched alkyl group having 1 to 6 carbon atoms, and X is 2 or 3. Representative examples of the methacryloyl group-containing alkoxysilane represented by formula (IV) include γ-methacryloyl Examples include xypropyltriethoxysilane, γ-methacryloylxyprobyltribroboxysilane, etc. In addition, vinyltrialkoxysilane has the following formula [(V) formula l
This is shown in . C)1. = C) ISi (OR”),
(V) In the present invention, among the vinyltrialkoxysilanes represented by the above formula (V), R1 has 1 to 1 carbon atoms.
Six pieces are desirable, and one to three pieces are particularly preferred. Suitable vinyltrialkoxysilanes are vinyltrimethoxysilane, vinyltriethoxysilane and vinyltripropoxysilane, of which vinyltrimethoxysilane and vinyltriethoxysilane are preferred. If these functional group-containing alkoxysilanes are heated to a high temperature, they will react with the carbon in the heat-resistant resin or thermoplastic resin, form 5i-C bonds, become mineralized, and prevent dripping. Such a functional group-containing alkoxysilane exhibits a great effect on flame retardancy and prevention of dripping. Particularly, the effect in combination with the above reaction product is remarkable. [F) Composition ratio The proportions of styrene compounds and imide compounds, which are copolymerization components of the heat resistant resin, in the total amount of the polymeric substance consisting of the heat resistant resin and the thermoplastic resin are 10 to 50% by weight, respectively, as a total amount. , 10-4511%
is preferred, particularly 12 to 45% by weight. If the total proportion of the styrene compound and imide compound in the polymeric substance is less than 10% by weight, the resulting composition will have poor heat resistance. On the other hand, if it exceeds 50% by weight, the processability of the resulting composition is poor. In addition, butadiene rubber, ethylene-propylene rubber, and acrylic acid, which are used in the production of rubber reinforcing materials and impact-resistant resins, which are used in the production of heat-resistant resin (2), which occupy polymeric substances, Ester rubber] (
The total amount of the rubber component (hereinafter referred to as "rubber component") is 5 to 35% by weight, preferably 5 to 30% by weight.
Particularly suitable is a weight of 5 to 25%. If the total proportion of the rubber component in the polymer substance is less than 5% by weight, the resulting composition will have poor impact resistance.On the other hand, if it exceeds 35% by weight, the moldability of the composition will be poor. Not only is it not good, but its heat resistance is also poor. Also, the composition ratio of antitonin oxide to 100 parts by weight of the polymeric substance is 0.5 to IO parts by weight. If the composition ratio of antimony oxide exceeds 10 parts by weight, the mechanical strength of the resulting composition will decrease. By using antimony oxide and the reaction product together, the flame retardance will be synergistically improved. Expressing a synergistic effect. In order to achieve the
．． 0 to 8.0 parts by weight is desirable. Furthermore, the composition ratio of the reaction product to 100 parts by weight of the polymeric substance is 5.0 to 40 parts by weight. Particularly preferably 5.0 to 35 parts by weight, if the composition ratio of the reaction product to ioo parts by weight of the polymeric substance is less than 5.0 parts by weight, a composition exhibiting sufficient flame retardancy cannot be obtained. On the other hand, if it exceeds 40 parts by weight, the cost will increase (and the impact resistance of the resulting composition will not be improved). Also, the ratio of the reaction product to 1 part by weight of antimony oxide is 1 to 5 parts by weight. The composition ratio of the functional group-containing alkoxysilane to 100 parts by weight of the polymeric substance is preferably 0.1 to 3.0 parts by weight, particularly preferably 0.1 to 2.5 parts by weight.
If the composition ratio of the functional group-containing alkoxysilane to 0.00 parts by weight of the polymeric material is less than 0.1 parts by weight, the composition will not be able to sufficiently exhibit the dripping prevention effect. On the other hand, if it exceeds 0.3 parts by weight, not only will slip occur during production of the composition, but the resulting composition will have poor heat resistance. iG) Composition production, molding method, etc. In producing the composition of the present invention, the heat-resistant resin and thermoplastic resin, which are polymeric substances, as well as antimony oxide, reaction products, and functional group-containing alkoxysilane are uniformly mixed. Although the purpose can be achieved by blending, there are many widely used stabilizers against heat, oxygen and light, fillers,
Additives such as colorants, lubricants, plasticizers, and antistatic agents may be added depending on the intended use of the composition, to the extent that the properties of the composition of the present invention are not essentially impaired. In producing the composition, all the components may be mixed at the same time (some of the components may be mixed in advance,
The resulting mixture and the remaining composition components may be mixed. Mixing methods include tri-blending using a mixer such as a Henschel mixer, which is commonly used in the field of synthetic resins, and mixing while melting using mixers such as oven rolls, extrusion mixers, Nigu and Banbury mixers. Here are some ways to do it. Among these mixing methods, two or more of these mixing methods may be used in combination to obtain a uniform composition (for example,
(pre-triblending and then melt-mixing the mixture). In particular, even when using tri-blend together or when using one or more melt-mixing methods, when producing a molded product using the molding method described below, it is important to use a pelletizer to produce pellets. is preferred. Of the above mixing methods, both melt kneading and molding using the molding method described below must be carried out at a temperature at which the polymeric substance used is melted. but,
If carried out at a high temperature, the polymer substance may undergo thermal decomposition or deterioration, or the reaction product may decompose, so it is necessary to carry out the process at a temperature below 280°C. The composition of the present invention may be molded into a desired shape by applying molding methods commonly practiced in the field of synthetic resins, such as injection molding, extrusion molding, compression molding, and blow molding. Alternatively, after forming the sheet into a sheet using an extrusion molding machine, this sheet may be formed into a desired shape by a secondary processing method such as a vacuum forming method or a pressure forming method. [Examples and Comparative Examples] Hereinafter, the present invention will be further explained with reference to Examples. In the Examples and Comparative Examples, the melt flow index (hereinafter referred to as rMIJ) is 721O according to JIS, and the temperature is 250 ℃ and a load of 5 kg.In addition, the tensile yield strength was measured using ASTM No. 1 dumbbells according to ASTI J Ro 638, and the strain rate was 5 a + a.
Measured at +/min. Furthermore, the Izotsu impact strength is A
Measurement was performed with a notch at a temperature of 23° C. according to STtl D256. In addition, in the heat resistance test, changes in the state of the sample were observed after it was left in a press at 250° C. for 60 minutes. In addition, the manufacturing method, type, physical properties, etc. of the heat-resistant resin, thermoplastic resin, impact-resistant resin, styrene copolymer resin, antimony oxide, bromine-containing material, and functional group-containing alkoxysilane used in the examples and comparative examples are as follows. Shown below. [(A) Heat-resistant resin J As the heat-resistant resin, heat-resistant resin (11) and heat-resistant resin (■) manufactured as follows were used. In a 1 of 2 autoclave, 6.000 g of water, 2.40 g.
Charged with 0 g styrene (ST), aoo g acrylonitrile (AN) and aoo g N-phenylmaleimide (N-PMI), plus 8 g lauryl peroxide and 9.6 g tert-butyl as initiators. Peroxylaurate, 8 g tertiary-dodecyl mercaptan (chain transfer agent) and 20 g as suspension stabilizer
g of tricalcium phosphate and 0.3 g of sodium dodecylbenzenesulfonate were added, and polymerization was carried out for 2 hours at a temperature of 80° C. with 1 stirring. Next, the temperature of the polymerization system was raised to 120° C., and after polymerization was carried out at this temperature for 3 hours, the polymerization system was allowed to cool to room temperature. the result,
Approximately 3,500 g of pale yellow powder was obtained. When the obtained powder was determined by infrared absorption spectroscopy (solution method), the weight ratio was ST: AN: N-PM I = 6.
The intrinsic viscosity of this heat-resistant resin was a terpolymer (hereinafter referred to as "heat-resistant resin (A)") with a ratio of 0: 20: 2G (in chloroform, temperature Q, O5g/5
0 tm12.30℃) [η] is 0.950, and the heat resistance temperature (18.5kg according to ASTM D64δ) is 0.950.
Measured under a load of (hereinafter the same) was 118°C. 2.400 g styrene (ST), 800 g acrylonitrile (AN) and N-phenylmaleimide (N
- Butadiene homopolymer rubber 2 having a Mooney viscosity (ML, 1, 100°C) of 35 in a monomer mixture of -PMI)
80 g of the rubber was charged and the rubber was completely dissolved in the monomer mixture. The temperature of the polymerization system was raised to 110°C, and bulk polymerization was carried out for 2.5 hours. The monomer mixture containing the obtained prepolymer was added to 6.000 g of water containing the same initiator, chain transfer agent, and suspension stabilizer as above at 80°C.
Aqueous suspension polymerization was carried out for 2 hours at a temperature of . The temperature of the polymerization system was immediately raised to 120° C., and aqueous suspension polymerization was carried out at this temperature for 3 hours, after which the polymerization system was allowed to cool to room temperature. As a result, approximately 3.300 g of yellow powder was obtained. When the obtained powder was analyzed in the same manner as the heat-resistant resin (1), it was found that the butadiene homopolymer rubber contained a kraft polymer (hereinafter referred to as "
It turned out to be an impact-resistant resin (b).
The intrinsic viscosity [η] of this heat-resistant resin (II) is 0.850
The heat resistant temperature was 108°C. f (b) Thermoplastic resin 1 Among thermoplastic resins, acrylonitrile-butadiene-styrene ternary copolymer resin (r
ABsJ), methyl methacrylate-butadiene-styrene ternary copolymer resin (hereinafter referred to as rMBsJ),
Acrylonitrile-acrylic acid ester rubber-styrene ternary copolymer resin (hereinafter referred to as rAASJ) and acrylonitrile-olefin rubber-styrene ternary copolymer resin (hereinafter referred to as rAESJ) are disclosed in JP-A-58-1, respectively.
ABSIllll, MBS resin, AASFjA used in the examples and comparative examples of J4144 publication specification
It was prepared and used in the same manner as resin and AES resin. In addition, as the styrene-based copolymer resin, an acrylonitrile-styrene copolymer (average degree of polymerization of about 750, hereinafter referred to as rASJ) with a copolymerization ratio of acrylonitrile of 23% by weight and a copolymerization ratio of methyl methacrylate of 25% by weight are used.
% by weight of a methyl methacrylate-styrene copolymer (average degree of polymerization of about 800, hereinafter referred to as rMSJ) was used. [(C) Antimony oxide J Furthermore, antimony dioxide (hereinafter referred to as r 5btOs J) was used as antimony oxide. [(D) Bromine-containing substance (reaction product, etc.) l Also, as a reaction product, the epoxy system represented by the above formula (■) has a bromine content of 52% by weight and an average epoxy equivalent of t, soo. 1000 g of the compound and 200 g of an acrylonitrile-butadiene copolymer having a carboxyl group at both ends with a molecular weight of 3500 and a copolymerization ratio of acrylonitrile of 17% by weight were dissolved in 2000 g of cellosolve acetate and stirred until uniform. did. Next, 0.5 g of imidazole was added to the reaction system, and the reaction system was
The temperature was raised to 50°C, and the reaction was carried out for 4 hours while stirring. The solvent was removed from the resulting solution by evaporation, and the solution was vacuum-dried. As a result, %1150g of light brown powder (hereinafter referred to as "bromine (A)") was obtained.
)” was obtained. For comparison, decabromobiphenyl ether (hereinafter referred to as "bromine compound (B)") and the same bromine-containing epoxy compound as used previously were also used.
Hereinafter, [referred to as bromine (C)] was used. [(E) Functional group-containing alkoxysilane] Furthermore, as the functional group-containing alkoxysilane, γ-mercaptopropyltrimethoxysilane

[hereinafter referred to as "silane (1)"] and γ-mercaptopropylmethyldimethoxysilane [
(hereinafter referred to as "compound (2)"), γ-methacroxypropyltrimethoxysilane (hereinafter referred to as "silane (3)"), and vinyltrimethoxysilane (hereinafter referred to as "silane (4)").
)” was used. Examples 1 to 12, Comparative Examples 1 to 6 Table 6 shows the types and amounts of heat-resistant resins, thermoplastic resins, bromine-containing substances, and functional group-containing alkoxysilanes (hereinafter referred to as "alkoxysilanes"). The respective compositional components and their respective blending amounts are shown in Table 1.Sb, 0. (antimony oxide) and 0.2 parts by weight of 2,6-di-tert-butyl-p-cresol (as a stabilizer) were each triblended for 5 minutes using a Henschel mixer. Each mixture obtained was heated to 200°C in cylinder 1 and 220°C in cylinder 2.
, 240℃ for cylinder 3, 240℃ for adapter
A pellet (composition) was produced using a vent-type twin-screw extruder (diameter: 30 mm) set at 230° C. while stirring the die. Measurement of Ml, tensile yield strength, isot impact strength (notched), and heat resistance temperature of each composition obtained, and flame retardance [test piece thickness 1.6 (1/16 inch)]
J and heat resistance tests were evaluated. These results are shown in Table 2. (Left below) From the results of the above Examples and Comparative Examples, it is clear that the resin composition obtained by the present invention not only has excellent flame retardancy and impact resistance, but also has good heat resistance. . [Effects of the Invention] That is, by combining a reaction product and a functional group-containing alkoxysilane, a resin composition with well-balanced physical properties can be obtained. Also, flame retardancy, especially dripping, is improved. The resin composition obtained by the present invention not only has excellent flame retardancy, impact resistance, and heat resistance, but also exhibits the following effects (characteristics). +11 Good moldability (fluidity). (2) Good gloss of the molded product. (3) Excellent weather resistance and little discoloration. Since the resin composition obtained by the present invention has the excellent characteristics described above, it can be used in various fields as described below. (1) Television receivers (2) Housings for facsimiles, word processors, microcomputers, printers, etc. (3) Parts for Class 8 fire alarms (4) Housings for electrical and electrical equipment

Claims (1)

[Scope of Claims] (A) (1) A copolymer of at least a styrene compound and an imide compound of α,β-unsaturated dicarboxylic acid, and (2) a styrene compound reinforced with a rubber reinforcing material and α , at least one heat-resistant resin selected from the group consisting of a copolymer of β-unsaturated dicarboxylic acid with an imide compound, (B) butadiene rubber, ethylene-propylene rubber, or acrylic ester rubber with styrene. at least one thermoplastic resin selected from the group consisting of an impact-resistant resin obtained by graft copolymerizing and acrylonitrile or styrene and methyl methacrylate, and a copolymer resin of styrene and acrylonitrile or styrene and methyl methacrylate, (C ) antimony oxide, (D) a bromine-containing epoxy compound having an epoxy equivalent of 450 to 7,000 and a bromine content of 5.0 to 52% by weight, and having a carboxyl group at both ends and a molecular weight of 1. ,000 to 10,000, and (E) at least one functional group selected from the group consisting of mercapto group-containing alkoxysilanes, methacryloyl group-containing alkoxysilanes, and vinyltrialkoxysilanes. It consists of group-containing alkoxysilane, and the proportion of the styrene compound and imide compound, which are copolymerization components of the heat-resistant resin, in the total amount of the heat-resistant resin and thermoplastic resin is 10 to 50% by weight, respectively. Yes, the proportion of imide compounds in the total amount of styrene compounds and imide compounds is 5.
~50% by weight, and the proportion of the rubber reinforcing material used in the production of heat-resistant resins and the butadiene rubber, ethylene-propylene rubber, and acrylic ester rubber used in the production of impact-resistant resins is the total amount of these. As 5~
The amount of antimony oxide is 35% by weight, and the amount of antimony oxide is 0.5 to 1% per 100 parts by weight of the total amount of heat-resistant resin and thermoplastic resin.
0 parts by weight, the reaction product is 5.0 to 40 parts by weight, and the functional group-containing alkoxysilane is 0.1 to 3.0 parts by weight.
Parts by weight of the resin composition.