JPH06192344A - Modified aromatic vinylic polymer and its composition - Google Patents

Abstract

PURPOSE:To obtain the subject polymer not generating a smell on its modification reaction and excellent in adhesivity to fillers, metals and ethylene/vinyl alcohol copolymer by reacting an aromatic vinyl compound polymer with a specific epoxy group-containing acrylamide monomer. CONSTITUTION:(A) An aromatic vinyl polymer (e.g. polystyrene, acrylonitrile- styrene copolymer resin) is reacted with (B) an epoxy group-containing acrylamide monomer of the formula (Ar is 6-24C aromatic hydrocarbon substituted with a glycidyloxy group; R is H, methyl) {e.g. N-[4-(2,3- epoxypropoxy)-3,5-dimethylbenzyl]acrylamide} to provide the objective polymer. The component B is produced e.g. by condensing a phenolic OH group-containing aromatic hydrocarbon with N-methylol (meth)acrylamide or its alkyl ether derivative in the presence of an acid catalyst and subsequently glycidylating the phenolic OH group of the condensation product.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a modified aromatic vinyl which has no odor during modification and is excellent in adhesiveness with a filler, a metal and an ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH). -Based polymer, and other thermoplastic resin having a functional group having reactivity with the modified aromatic vinyl-based polymer and an epoxy group, etc., especially mechanical properties such as Izod impact strength, tensile strength and elongation The present invention relates to a modified aromatic vinyl polymer composition having excellent physical properties.

[0002]

2. Description of the Related Art Aromatic vinyl polymers such as polystyrene and ABS (acrylonitrile-butadiene-styrene copolymer) have excellent physical properties and are widely used as molding materials. Further, in order to improve heat resistance and rigidity, reinforcement with a filler such as glass fiber is performed. However, since the aromatic vinyl polymer does not have a reactive functional group, there is a problem that the adhesion with the glass fiber is poor and the reinforcing effect is not sufficient. In order to compensate for this drawback, an unsaturated carboxylic acid, glycidyl methacrylate (hereinafter abbreviated as GMA), or an epoxy group-containing vinyl monomer such as allyl glycidyl ether was copolymerized with a styrene monomer. It has been proposed to use a so-called modified styrene resin (for example, Japanese Patent Publication No. 57-37).
165).

According to this method, a strong chemical bond is formed between the glass fiber and the carboxyl group or epoxy group, and excellent adhesion is exhibited between the glass fiber and the styrene resin. In the system using the resin, the reinforcing effect of the glass fiber is improved. However, these modified styrenic resins are produced from the polymerization step, and thus there is a problem that the cost is increased because new production equipment is required.

Further, since these modified styrenic resins are produced in an extruder, when they are kneaded with an unsaturated carboxylic acid or GMA in an extruder, in the case of an unsaturated carboxylic acid, the metal of the screw of the extruder is corroded. In addition, there are various problems such as GMA and the like, which has a low boiling point and may generate an offensive odor due to the high temperature during extrusion, resulting in poor workability.

Further, since the aromatic vinyl polymer is excellent in mechanical strength, low cost, etc., it is used in combination with a polyester resin, a polyphenylene sulfide resin, a polycarbonate resin, a nylon resin, and an ethylene-acrylic acid ester copolymer. Blends are being considered. However, originally, the compatibility between the aromatic vinyl polymer and each of the above resins is generally poor, so that the Izod impact strength, the tensile strength, the elongation, etc. are remarkably reduced, which is far from practical use.

[0006]

DISCLOSURE OF THE INVENTION The present invention is free from the above-mentioned problems and drawbacks, and does not cause an offensive odor during denaturation.
A modified aromatic vinyl-based polymer having excellent adhesiveness to fillers, metals, and EVOH, and a thermoplastic resin having a functional group capable of reacting with the modified aromatic vinyl-based polymer and an epoxy group. In particular, it is an object of the present invention to provide a thermoplastic resin composition having excellent mechanical properties such as Izod impact strength, tensile strength and elongation, and a good balance among the physical properties.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific epoxy group-containing acrylamide monomer is present in an aromatic vinyl polymer as a radical generator. It was found that the resin obtained by the reaction below can achieve the above-mentioned object, and completed the present invention.

That is, basically, the present invention relates to "1) an aromatic vinyl polymer A, and the following general formula (I):

[0009]

Embedded image An epoxy group-containing acrylamide monomer B represented by H ₂ C═CR—CO—NH—CH ₂ —Ar (I) (wherein Ar is a carbon number substituted with at least one glycidyloxy group). A modified aromatic vinyl polymer, which is obtained by reacting 6 to 24 aromatic hydrocarbon groups, and R represents a hydrogen atom or a methyl group.

2) A modified aromatic vinyl polymer composition comprising a modified aromatic vinyl polymer and an additive,
The modified aromatic vinyl-based polymer is the modified aromatic vinyl-based polymer C described in 1 above, and the additive is a filler D.
And a composition condition thereof is that the filler D is 3 to 300 parts by weight with respect to 100 parts by weight of the modified aromatic vinyl polymer C. Composition.

3) It is obtained by further adding a radical generator H to the aromatic vinyl polymer A and the epoxy group-containing acrylamide monomer B represented by the general formula (I) and reacting them in an extruder. The modified aromatic vinyl polymer according to item 1 above, wherein

4) A modified aromatic vinyl polymer composition comprising a modified aromatic vinyl polymer and additives,
The modified aromatic vinyl-based polymer is the modified aromatic vinyl-based polymer according to the above item 3, the additive is the filler D, and the composition condition thereof is that of the aromatic vinyl-based polymer A. 0.01 to 20 parts by weight of the epoxy group-containing acrylamide monomer B, 0 to 5 parts by weight of the radical generator H and 3 to 300 parts by weight of the filler D per 100 parts by weight, and A modified aromatic vinyl polymer composition, which is obtained by melt-kneading. Is disclosed.

Specific examples of the aromatic vinyl polymer used in the present invention include polystyrene, high-impact polystyrene, acrylonitrile-styrene resin,
ABS resin etc. can be mentioned.

The epoxy group-containing acrylamide monomer used in the present invention has the following general formula (I).

[0015]

Embedded image H ₂ C═CR—CO—NH—CH ₂ —Ar (I) (wherein Ar represents an aromatic hydrocarbon group having 6 to 24 carbon atoms and substituted with at least one glycidyloxy group). ,
R represents a hydrogen atom or a methyl group. ).

For example, an aromatic hydrocarbon having at least one phenolic hydroxyl group, N-methyl acrylamide, or N-methyl methacrylamide,
Alternatively, it can be easily obtained by condensing an alkyl ether derivative of N-methylolacrylamide or N-methylolmethacrylamide with an acid catalyst and then glycidylating a phenolic hydroxyl group.

Specific examples of the epoxy group-containing acrylamide monomer include N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide and N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide.
-[4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] methacrylamide, N- [4- (2,2
3-epoxypropoxy) -3-methylbenzyl] acrylamide and the like can be mentioned.

The filler used in the present invention includes metals such as iron, aluminum, copper, lead, zinc, tin and nickel, and alloys containing them as a main component (for example,
In addition to metal materials such as stainless steel, copper, brass) and various metal oxides, glass, carbon fiber, carbon black, silicon carbide fiber, carbon whiskers, asbestos, graphite, magnesium carbonate, calcium carbonate, clay, mica, talc, Inorganic or organic materials such as silica, barium sulfate, alumina, inorganic pigments, wood flour, pulp, polyester fibers and the like can be mentioned.

Suitable composition conditions of each component of the filler-reinforced aromatic vinyl polymer composition of the present invention are modified aromatic vinyl polymer and the modified aromatic vinyl polymer and aromatic vinyl polymer. The filler is 3 to 300 parts by weight, preferably 5 to 200 parts by weight, based on 100 parts by weight of the resin composition consisting of. When the addition amount of the filler is less than the above range, a sufficient effect of improving physical properties cannot be obtained, and when the addition amount is large, the resin is colored,
It is not preferable because the impact strength is lowered.

The method for producing the filler-reinforced aromatic vinyl polymer composition of the present invention is not particularly limited, and a generally known method can be adopted. For example, an aromatic vinyl polymer, an epoxy group-containing acrylamide monomer, a radical generator, and a filler are uniformly mixed using a high-speed stirrer, and then melted with a uniaxial or multiaxial extruder having sufficient kneading ability. It is manufactured by kneading. Further, the filler-reinforced aromatic vinyl polymer composition of the present invention is an aromatic vinyl polymer,
Epoxy group-containing acrylamide monomer, radical generator, method of melting and kneading filler at the same time, method of adding filler only later, or filler as aromatic vinyl polymer, epoxy group-containing acrylamide monomer , And a radical generator as a molten composition.

The functional group in the thermoplastic resin having a functional group capable of reacting with the epoxy group used in the present invention includes a carboxyl group and a salt thereof, an anhydrous carboxyl group, a hydroxyl group, a mercapto group, an epoxy group,
Known functional groups such as amino groups can be mentioned. As the basic structure of the thermoplastic resin, polyolefin, polyamide, polyester, polyurethane, polyphenylene or the like can be used.

As the thermoplastic resin having a functional group capable of reacting with an epoxy group, a polyester resin, a polyphenylene sulfide resin, a polycarbonate resin, a nylon resin, a polyurethane, a copolymer of ethylene and acrylic acid or an acrylic ester, Examples thereof include polyolefins modified with unsaturated carboxylic acids and polystyrene modified with unsaturated carboxylic acids.

The polyester resin used in the present invention is a polyester having an aromatic ring as a chain unit of the polymer and is a polymer or copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid and a diol as main components. is there.
Examples of preferred aromatic polyester resins in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene terephthalate elastomers. For example, Hytrel (trade name) manufactured by Toray-Dupont Co., Ltd. may be mentioned.

The polyphenylene sulfide resin (hereinafter abbreviated as PPS) used in the present invention includes a cross-linked PPS which requires cross-linking after polymerization to have a high molecular weight, and a high-molecular weight linear PPS at the time of polymerization. Examples of commercially available cross-linked PPS include Ryton P-6 (manufactured by Phillips Petroleum Co., Ltd.), and examples of linear PPS include FORTRON W-205 (manufactured by Kureha Chemical Industry Co., Ltd.). The PPS resin used in the present invention may be either a cross-linked PPS or a linear PPS.

The polycarbonate resin used in the present invention is a compound known per se. In general, they are prepared by reacting dihydric phenols with carbonate precursors, such as phosgene, halogen formates or carbonate esters. Homopolymers derived from bisphenol A are preferably used in the present invention.

The nylon resin used in the present invention is also referred to as polyamide resin, and examples thereof include nylon 6, nylon 66, nylon 46, nylon 11 and nylon 12. Among them, nylon 6 and nylon 66 are heat resistant and molded. It is preferable from the viewpoint of sex.

The polyurethanes used in the present invention are those generally made from diisocyanates, polyesters or polyethers and chain extenders. These polyurethanes are substantially linear and have thermoplastic processability.

The copolymer of ethylene and acrylic acid or acrylic acid ester used in the present invention is an acrylic acid ester of ethylene such as methyl acrylate and ethyl acrylate, and methacrylic acid ester such as methyl methacrylate and ethyl methacrylate. , Copolymerized with one or more comonomers of acrylic acid or methacrylic acid. Preferred are the well-known copolymers of ethylene and acrylic acid ester, and particularly preferred are the ethylene-ethyl acrylate copolymers. The ethylene portion in the copolymer is preferably in the range of about 70 to 90% by weight.

The unsaturated carboxylic acid-modified polyolefin used in the present invention is obtained by reacting polyolefin with a predetermined amount of unsaturated carboxylic acid in the presence of a radical generator. Examples of the polyolefin include polypropylene, polyethylene, propylene-ethylene block or random copolymer, ethylene-propylene elastomer, ethylene-propylene-
Examples thereof include diene elastomers, ethylene-propylene dicyclopentadiene copolymers, ethylene-propylene-ethylidene norbornene copolymers, and poly (4-methyl-pentene-1). Further, each of the resins listed above can be used in combination.

Examples of the unsaturated carboxylic acids include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, and acid anhydrides and esters thereof, with maleic anhydride being particularly preferred. preferable.
As the radical generator, the same ones as those used for the modification of the aromatic vinyl polymer can be used as described later.

Examples of the polystyrene modified with unsaturated carboxylic acids used in the present invention include styrene-unsaturated carboxylic acid copolymers and the like. These include styrene and unsaturated carboxylic acids according to a conventionally known method. It can be obtained by copolymerization. Examples of the unsaturated carboxylic acids are the same as the above-mentioned unsaturated carboxylic acids. As the polymerization method, any of the bulk polymerization method and the solution polymerization method can be used, and the polymerization can be carried out in a single polymerization tank, but the polymerization is continuously carried out by arranging a plurality of polymerization tanks in series. It is preferable to carry out in multiple stages.

Examples of the other thermoplastic resin constituting the modified aromatic vinyl polymer composition used in the present invention include polyacetal resin, polyphenylene oxide resin, polyarylate resin and polysulfone resin. Modified aromatic vinyl polymer constituting thermoplastic resin composition, resin composition comprising the modified aromatic vinyl polymer and aromatic vinyl polymer, and thermoplastic having functional group capable of reacting with epoxy group The composition conditions of the resin are modified aromatic vinyl-based polymer and resin composition consisting of the modified aromatic vinyl-based polymer and the aromatic vinyl-based polymer, 5 to 95 parts by weight, preferably 10 to 90 parts by weight, epoxy. The thermoplastic resin having a functional group capable of reacting with the group is in the range of 95 to 5 parts by weight, preferably 90 to 10 parts by weight.

There is no particular limitation on the method for producing the thermoplastic resin composition of the present invention, and a generally known method can be adopted. For example, a modified aromatic vinyl-based polymer and a resin composition comprising the modified aromatic vinyl-based polymer and the aromatic vinyl-based polymer, a thermoplastic resin having a functional group capable of reacting with an epoxy group, a high-speed stirrer, etc. After being uniformly blended by using, it is produced by melt-kneading with a uniaxial or multiaxial extruder having a sufficient kneading ability.

Further, an aromatic vinyl polymer, a thermoplastic resin having a functional group capable of reacting with an epoxy group, an epoxy group-containing acrylamide monomer, and a radical generator are uniformly mixed at the same time, and then melt-kneaded in an extruder. It can also be manufactured. Also, depending on the purpose, various elastomers, pigments, dyes,
Add reinforcing materials such as glass fiber, metal, carbon fiber, talc, filler such as calcium carbonate, antioxidant, ultraviolet absorber, lubricant, flame retardant, and antistatic agent, conductive filler such as carbon black, etc. be able to.

As the radical generator used in the present invention, compounds known as radical polymerization initiators are used. Specific examples thereof include t-butylperoxybenzoate, dicumylperoxide and 2,5- Dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene-3
Examples thereof include organic peroxides represented by, for example, azobisisobutyronitrile, azobisisovaleronitrile, and other azobisnitrile compounds, and benzoimperoxide, organic peracid compounds.

Suitable composition conditions of the above respective components are as follows: 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, of epoxy group-containing acrylamide monomer, and radical generation relative to 100 parts by weight of aromatic vinyl polymer. Agent 0 to 5 parts by weight, preferably 0 to
1 part by weight. When the addition amount of the epoxy group-containing acrylamide monomer is less than the above range, a sufficient effect of improving the physical properties cannot be obtained, and when the addition amount of the epoxy group-containing acrylamide monomer and the radical generator is large, the resin is This is not preferable because it causes coloration and a decrease in molecular weight.

Further, a stabilizer such as an antioxidant, a slip agent, an ultraviolet absorber, an antistatic agent, a nucleating agent and the like can be added to the modified aromatic vinyl polymer of the present invention. The method for producing the modified aromatic vinyl polymer in the present invention is not particularly limited, and a generally known method can be adopted.

For example, it is produced by reacting a specific epoxy group-containing acrylamide monomer, a radical generator, and an aromatic vinyl polymer in an organic solvent with stirring at the decomposition temperature of the radical generator. Also, an aromatic vinyl polymer,
It is manufactured by uniformly mixing the epoxy group-containing acrylamide monomer and the radical generator with a high-speed stirrer and the like, and then melt-kneading with a uniaxial or multiaxial extruder having sufficient kneading ability. The reaction temperature in the extruder is preferably 150 to 250 ° C, and the reaction time is preferably 0.5 to 30 minutes. In the present invention, it is preferable to produce the modified aromatic vinyl polymer with an extruder in terms of economy.

The modified aromatic vinyl polymer of the present invention may be used in the form of a composition containing an unmodified aromatic vinyl polymer. The content of the unmodified aromatic vinyl polymer is 0 to 95% by weight, preferably 0 to 80% by weight.

[0040]

EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. The physical property evaluations described in Examples and Comparative Examples were based on the following methods.

(1) Odor upon modification with an aromatic vinyl polymer: An unpleasant odor that was generated during extrusion was regarded as a strange odor, and an odor during extrusion was odorless. (2) Izod impact strength: JIS -K7110 (3) Tensile strength and elongation: JIS-K7113 (4) Peel strength: Soft aluminum plate (hereinafter abbreviated as "Al plate") degreased with modified aromatic vinyl polymer, steel plate or EVOH Heated and pressed on the sheet to adhere, and using a tensile tester, measure the coating film from one end of a strip test piece with a width of 10 mm at a temperature of 23 ° C, a peeling angle of 180 degrees, and a pulling speed of 50 mm / min.
The peeling strength was measured in accordance with JIS-K7207. (5) Deflection temperature under load (heat resistance)
Kgf / cm ² ) (6) Bending elastic modulus Based on JIS-K7113.

Examples 1 to 4 Polystyrene resin as an aromatic vinyl polymer: Topolex 550-0 (trade name, manufactured by Mitsui Toatsu Chemicals, Inc.)
5, N- as the epoxy group-containing acrylamide monomer
[4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide: manufactured by Kanegafuchi Chemical Co., Ltd.
Dicumyl peroxide was used as a radical generator in Table 1.
After thoroughly blending with a Henschel mixer at the ratio shown in,
A modified polystyrene resin was obtained by extruding into pellets at a melting temperature of 200 ° C. and a screw rotation speed of 100 rpm with a twin-screw extruder having a screw diameter of 30 mm and L / D = 30.

The obtained modified polystyrene resin is an Al plate,
The peel strength was measured on the steel sheet and the EVOH sheet after melt-pressing at a temperature of 220 ° C. so that the thickness was 200 μm and bonding. The results are shown in Table 1 together with the odor during extrusion. It can be seen that odor is hardly generated during extrusion, and that it has sufficient peel strength, and that the adhesiveness is good.

Comparative Examples 1 and 2 The same as Examples 1 to 4 except that the radical generator was 10 parts (Comparative Example 1) and the epoxy group-containing acrylamide monomer was not added (Comparative Example 2). . The peel strength was measured in the same manner as in Examples 1 to 4 using the obtained polystyrene resin. The results are shown in Table 1 together with the odor during extrusion. Almost no odor was generated during extrusion, but the peel strength was low and the adhesiveness was poor.

Comparative Example 3 The same procedure as in Example 3 was repeated except that the epoxy group-containing acrylamide monomer was changed to allyl glycidyl ether (AGE). The results are shown in Table 1. An unpleasant odor was generated during extrusion, which was not preferable and the peel strength was low. That is, the heat resistance or the peel strength / adhesiveness was poor, which was not preferable.

Examples 5 to 8 As an aromatic vinyl polymer, ABS resin: Santak ST52, trade name, manufactured by Mitsui Toatsu Chemicals, Inc., and N- [4- (2,2,6] as an epoxy group-containing acrylamide monomer. 3-
Epoxypropoxy) -3,5-dimethylbenzyl] methacrylamide: manufactured by Kanegafuchi Chemical Co., Ltd. 1,3-bis- (t-butylperoxy-isopropyl) benzene as a radical generator at a ratio shown in Table 2. A modified ABS resin was obtained by extrusion pelletization in the same manner as in Example 1.

The modified ABS resin thus obtained was used as an Al plate, a steel plate,
And the temperature is 220 ℃ on EVOH sheet and the thickness is 20
Peel strength was measured after melt-pressing and bonding to 0 μm. The results such as odor during extrusion are shown in Table 2. These had almost no odor during extrusion, sufficient peel strength, and good adhesiveness.

Comparative Examples 4 to 5 The same as Examples 5 to 8 except that the radical generator was 10 parts (Comparative Example 4) and the epoxy group-containing acrylamide monomer was not added (Comparative Example 5). . The peel strength was measured in the same manner as in Examples 1 to 4 using the obtained ABS resin. The results are shown in Table 2 together with the offensive odor during extrusion.
These had almost no offensive odor during extrusion, but had low peel strength and poor adhesiveness, which was not preferable.

Comparative Example 6 The same procedure as in Example 7 was repeated except that the epoxy-containing acrylamide monomer was changed to glycidyl methacrylate (GMA). The results are shown in Table 2. An offensive odor was generated during extrusion, and the peel strength was low and the adhesiveness was poor.

Examples 9 to 12 ABS resin as an aromatic vinyl polymer: Santak UT-61, trade name, manufactured by Mitsui Toatsu Chemicals, Inc., N- [4- ( A few
-Epoxypropoxy) -3,5-dimethylbenzyl]
Acrylamide: manufactured by Kanegafuchi Chemical Co., Ltd. As a radical generator, dicumyl peroxide and glass chopped strands having a length of 3 mm were sufficiently blended in a tumbler at a ratio shown in Table 3, and then screw diameter was 30 mm, L / D. ＝ 30 twin screw extruder Melting temperature 240 ℃ Screw-rotation speed 100rp
Extruded into pellets at m 2.

The pellets were injection-molded at a cylinder temperature of 240 ° C., and the physical properties of the pellets were tested.
The results are shown in Table 3. These had almost no offensive odor during extrusion, had a good balance between mechanical properties, and were sufficiently suitable for practical use.

Comparative Examples 7 to 8 Comparative Examples 7 to 8 were the same as Examples 9 to 12, except that the epoxy group-containing acrylamide monomer or the radical generator was mixed in a different amount from the resin composition of the present invention. The results are shown in Table 3. These are unfavorable for practical use because they have poor mechanical property balance.

Comparative Example 9 The same procedure as in Example 9 was carried out except that maleic anhydride (MAH) was used instead of the epoxy group-containing acrylamide monomer. The results are shown in Table 3. Compared with the case where the epoxy group-containing acrylamide monomer was used, the balance of mechanical properties was poor, and an unpleasant odor was generated during extrusion, which was not preferable.

Examples 13 to 18 Polybutylene terephthalate as a polyester resin: TRB-H manufactured by Teijin Ltd. and polybutylene terephthalate elastomer: Hytrel 5557 manufactured by Toray-Dupont Co., Ltd., aromatic ABS resin as vinyl polymer: Santak ST-52 manufactured by Mitsui Toatsu Chemicals, Inc., and N- [4- (2,3-epoxypropoxy) -3,5 as epoxy group-containing acrylamide monomer. -Dimethylbenzyl] acrylamide, and 1,3-bis- (t-butylperoxy-isopropyl) benzene as a radical generator were mixed in a Henschel mixer at a mixing ratio shown in Table 4, and then the results of Examples 9 to
The same extruder as that of No. 12 was used to extrude pellets at a melting temperature of 250 ° C. and a screw rotation speed of 100 rpm.

The pellets were injection-molded at a cylinder temperature of 250 ° C., and a physical property test was conducted using the test pieces produced. The results are shown in Table 4. These had good balance of mechanical properties and were practically preferable.

Comparative Examples 10 to 13 The same as Examples 13 to 18 except that the mixing ratio of each raw material was changed as shown in Table 4, and the results are shown in Table 4. These were inferior in balance between mechanical properties and could not be put to practical use.

Examples 19 to 21 High-impact polystyrene resin as an aromatic vinyl polymer: 100 parts by weight of Topolex 830-05, trade name, manufactured by Mitsui Toatsu Chemicals, Inc., N as an epoxy group-containing acrylamide monomer After blending 1 part by weight of-[4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide in a Henschel mixer, Example 9
Extruded in pellets at a melting temperature of 200 ° C. and a screw rotation speed of 100 rpm with the same extruder as that of No. 12 to obtain a modified high-impact polystyrene resin. The modified high-impact polystyrene resin and the high-impact polystyrene resin and polybutylene terephthalate: TRB-H, trade name, manufactured by Teijin Limited at a ratio shown in Table 5 in the twin-screw extruder at a melting temperature of 250 ° C. and a screw rotation speed. Extruded pellets were obtained at 100 rpm.

The pellets were injection-molded at a cylinder temperature of 250 ° C. to prepare test pieces, and the physical properties were tested by the above-mentioned methods.
The results are shown in Table 5. Each of them had a good balance of mechanical properties, which was enough for practical use.

Comparative Examples 14 to 16 Physical properties tests were conducted in the same manner as in Examples 19 to 21 except that the modified high-impact polystyrene resin was not used, and the results are shown in Table 5. These have a remarkably poor balance of mechanical properties and cannot be put to practical use.

Examples 22 to 24 Polystyrene resin as an aromatic vinyl polymer: Topolex 550-05, trade name, manufactured by Mitsui Toatsu Chemicals, Inc.
100 parts by weight of N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide
Parts by weight and 0.3 parts by weight of 1,3-bis- (t-butylperoxy-isopropyl) benzene were mixed in a Henschel mixer, and then pelletized at a melting temperature of 200 ° C. and a screw rotation speed of 100 rpm in the twin-screw extruder. To obtain a modified polystyrene resin. The modified polystyrene resin and the polystyrene resin and polycarbonate: Panlite L-1225 (trade name, manufactured by Teijin Kasei Co., Ltd.) were extruded in the ratio shown in Table 6 by the twin-screw extruder at a melting temperature of 250 ° C. and a screw rotation speed of 100 rpm. Pellets were obtained.

The pellets were injection-molded at a cylinder temperature of 250 ° C. to prepare test pieces, and the physical properties were tested by the above-mentioned methods.
The results are shown in Table 6. Each of them had a good balance of mechanical properties, which was enough for practical use.

Comparative Examples 17 to 19 Physical properties tests were conducted in the same manner as in Examples 22 to 24 except that the modified polystyrene resin was not used, and the results are shown in Table 6. In all cases, the balance of mechanical properties was so bad that they could not be put to practical use.

Examples 25 to 27 As an aromatic vinyl polymer, ABS resin: 100 parts by weight of Santak ST-52, trade name, manufactured by Mitsui Toatsu Chemicals, Inc., N- [4- (2,3-epoxy] Propoxy) -3,
After blending 3 parts by weight of 5-dimethylbenzyl] acrylamide with a Henschel mixer, it was extruded into pellets with the twin screw extruder at a melting temperature of 210 ° C. and a screw rotation speed of 100 rpm to obtain a modified ABS resin. The modified ABS resin and the ABS resin and polyphenylene sulfide resin: trade name FORTRON W-205 manufactured by Kureha Chemical Industry Co., Ltd. in the ratio shown in Table 7 in the twin-screw extruder at a melting temperature of 310 ° C. and a screw rotation speed of 100 rpm. To obtain extruded pellets.

The physical properties of the pellets were injection-molded at a cylinder temperature of 280 ° C. and the physical properties were tested by the methods described above. The results are shown in Table 7. These had sufficiently good balance of mechanical properties for practical use.

Comparative Examples 20 to 22 In Examples 25 to 27, physical property tests were conducted in the same manner except that the modified ABS resin was not used, and the results are shown in Table 7. These have a remarkably poor balance of mechanical properties and cannot be put to practical use.

Examples 28 to 30 As an aromatic vinyl polymer, high-impact polystyrene resin: 100 parts by weight of Topolex 850-05, trade name, manufactured by Mitsui Toatsu Chemicals, Inc., N- [4- (2, After blending 1 part by weight of 3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide with a Henschel mixer, it was extruded into pellets with the twin screw extruder at a melting temperature of 200 ° C. and a screw rotation speed of 100 rpm to obtain a modified high An impact polystyrene resin was obtained. The modified high-impact polystyrene resin and the high-impact polystyrene resin and nylon resin: product name T-802 manufactured by Toyobo Co., Ltd.
The melting temperature is 250 in the above twin-screw extruder at the ratio shown in Table 8.
Extruded pellets were obtained at a temperature of ℃ and a screw rotation speed of 100 rpm.

Physical properties of the pellets were injection-molded at a cylinder temperature of 250 ° C., and the physical properties were tested by the methods described above. The results are shown in Table 8. These had sufficiently good balance of mechanical properties for practical use.

Comparative Examples 23 to 25 Physical properties tests were conducted in the same manner as in Examples 28 to 30 except that the modified high-impact polystyrene resin was not used, and the results are shown in Table 8. These have a remarkably poor balance of mechanical properties and cannot be put to practical use.

Examples 31 to 33 As the aromatic vinyl polymer, high-impact polystyrene resin: 100 parts by weight of Topolex 855-05, trade name, manufactured by Mitsui Toatsu Chemicals, Inc., N- [4- (2, After blending 1 part by weight of 3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide with a Henschel mixer, it was extruded into pellets with the twin screw extruder at a melting temperature of 200 ° C. and a screw rotation speed of 100 rpm to obtain a modified high An impact polystyrene resin was obtained. The modified high-impact polystyrene resin and the high-impact polystyrene resin and polyurethane resin: Elastollan C-90A (trade name, manufactured by Takeda Birdish Urethane Co., Ltd.) at the ratio shown in Table 9 are melted in the twin screw extruder at a melting temperature of 250. Extruded pellets were obtained at a temperature of ℃ and a screw rotation speed of 100 rpm.

The physical properties of the pellets were injection-molded at a cylinder temperature of 250 ° C. and the physical properties were tested by the above-mentioned methods. The results are shown in Table 9. These had sufficiently good balance of mechanical properties for practical use.

Comparative Examples 26 to 28 In Examples 31 to 33, physical property tests were conducted in the same manner except that the modified high-impact polystyrene resin was not used, and the results are shown in Table 9. These have a remarkably poor balance of mechanical properties and cannot be put to practical use.

Examples 34 to 36 Polystyrene resin as an aromatic vinyl polymer: Topolex 550-05, trade name, manufactured by Mitsui Toatsu Chemicals, Inc.
100 parts by weight of N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide
After blending parts by weight with a Henschel mixer, a modified polystyrene resin was obtained by extruding into a pellet with the twin screw extruder at a melting temperature of 200 ° C. and a screw rotation speed of 100 rpm. This modified polystyrene resin and the polystyrene resin and ethylene-ethyl acrylate copolymer: Union Carbide Co., Ltd. trade name DPD6169 at a ratio shown in Table 10 in the twin screw extruder at a melting temperature of 230 ° C. and a screw rotation speed. Extruded pellets were obtained at 100 rpm.

The pellets were injection-molded at a cylinder temperature of 230 ° C. to prepare test pieces, and the physical properties were tested by the above-mentioned methods.
The results are shown in Table 10. All of them had a good balance of mechanical properties sufficient for practical use.

Comparative Examples 29-31 In Examples 34-36, physical property tests were conducted in the same manner except that the modified polystyrene resin was not used, and the results are shown in Table 10. In all cases, the balance of mechanical properties was so bad that they could not be put to practical use.

Examples 37 to 39 As the aromatic vinyl polymer, ABS resin: 100 parts by weight of Santak ST-61, trade name, manufactured by Mitsui Toatsu Chemicals, Inc., N- [4- (2,3-epoxy] Propoxy) -3,
After blending 3 parts by weight of 5-dimethylbenzyl] acrylamide with a Henschel mixer, it was extruded into pellets with the twin screw extruder at a melting temperature of 210 ° C. and a screw rotation speed of 100 rpm to obtain a modified ABS resin.

As the unsaturated carboxylic acid modified polyolefin resin, polypropylene resin: 100 parts by weight of Mitsui Noblen JS-G, trade name, manufactured by Mitsui Toatsu Chemicals, Inc., 1 part by weight of maleic anhydride, 1,3- Bis- (t-
After blending 0.05 part by weight of butylperoxy-isopropyl) benzene with a Henschel mixer, it was extruded into pellets with the twin screw extruder at a melting temperature of 200 ° C. and a screw rotation speed of 100 rpm to obtain a maleic anhydride-modified polypropylene resin. . The maleic anhydride-modified polypropylene resin, the modified ABS resin, and the ABS resin were extruded in the proportions shown in Table 11 by the twin-screw extruder at a melting temperature of 230 ° C. and a screw rotation speed of 100 rpm to obtain pellets.

The physical properties of the pellets were injection-molded at a cylinder temperature of 230 ° C. by the above-mentioned method, and the results are shown in Table 11. These had sufficiently good balance of mechanical properties for practical use.

Comparative Examples 32 to 34 In Examples 37 to 39, physical property tests were conducted in the same manner except that the modified ABS resin was not used, and the results are shown in Table 11. These have a remarkably poor balance of mechanical properties and cannot be put to practical use.

Examples 40 to 42 High-impact polystyrene resin as an aromatic vinyl polymer: 100 parts by weight of Topolex 830-05, trade name, manufactured by Mitsui Toatsu Chemicals, Inc., N as an epoxy group-containing acrylamide monomer. After blending 1 part by weight of [-(4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide and 0.1 part by weight of dicumylperoxide in a Henschel mixer, the same extrusion as in Examples 9 to 12 was performed. A modified high-impact polystyrene resin was obtained by extruding into pellets at a melting temperature of 200 ° C and a screw rotation speed of 100 rpm in a machine. The modified high-impact polystyrene resin and the high-impact polystyrene resin and unsaturated carboxylic acid-modified polystyrene: DYLARK332, trade name, manufactured by ARCO CHEMICAL CO., LTD.
With a screw extruder, melt temperature 230 ℃, screw rotation speed 100rpm
To obtain extruded pellets.

The pellets were injection-molded at a cylinder temperature of 230 ° C. to prepare test pieces, and the physical properties were tested by the above-mentioned methods.
The results are shown in Table 12. All of them had a good balance of mechanical properties sufficient for practical use.

Comparative Examples 35-37 Physical properties tests were conducted in the same manner as in Examples 40-42 except that the modified high-impact polystyrene resin was not used, and the results are shown in Table 12. These have a remarkably poor balance of mechanical properties and cannot be put to practical use.

Examples 43 to 45 ABS resin: 100 parts by weight of Santak UT-61 manufactured by Mitsui Toatsu Chemicals, Inc., N- [4- (2,3-epoxypropoxy) -3,5-dimethyl After blending 2 parts by weight of benzyl] acrylamide with a Henschel mixer, a modified ABS resin was obtained in the same manner as in Examples 37 to 39. The modified ABS resin and the ABS resin and polybutylene terephthalate resin: trade name T manufactured by Teijin Ltd.
RB-H and glass chopped strands having a length of 3 mm as an inorganic filler were extruded at the ratio shown in Table 13 by the twin-screw extruder at a melting temperature of 260 ° C. and a screw rotation speed of 100 rpm to obtain pellets.

This pellet was injection-molded at a cylinder temperature of 260 ° C. to give a test piece, and a physical property test was conducted using this test piece.
The results are shown in Table 13. All of them had a good balance of mechanical properties sufficient for practical use.

Comparative Examples 38 to 40 Physical properties tests were conducted in the same manner as in Examples 43 to 45 except that the modified ABS resin was not used, and the results are shown in Table 13. These have a remarkably poor balance of mechanical properties and cannot be put to practical use.

[0085]

Industrial Applicability According to the present invention, a modified aromatic vinyl polymer and a resin composition thereof, which are excellent in balance between mechanical properties, particularly mechanical properties, and are excellent in moldability and adhesiveness, are provided. It can be widely used in various fields such as home electric appliances and industrial parts, etc.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

[0090]

[Table 5]

[0091]

[Table 6]

[0092]

[Table 7]

[0093]

[Table 8]

[0094]

[Table 9]

[0095]

[Table 10]

[0096]

[Table 11]

[0097]

[Table 12]

[0098]

[Table 13]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 67/02 LPB 8933-4J 69/00 LPN 9363-4J 77/00 LQS 9286-4J

Claims (14)

[Claims] 1. An aromatic vinyl polymer A having an epoxy group-containing acrylamide monomer represented by the following general formula (I): H ₂ C═CR—CO—NH—CH ₂ —Ar (I) Form B (wherein Ar represents an aromatic hydrocarbon group having 6 to 24 carbon atoms substituted with at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group) A modified aromatic vinyl polymer characterized by: 2. The modified aromatic vinyl polymer according to claim 1, wherein the aromatic vinyl polymer A is polystyrene. 3. The aromatic vinyl polymer A is ABS.
The modified aromatic vinyl polymer according to claim 1, which is a resin. 4. A modified aromatic vinyl-based polymer composition comprising a modified aromatic vinyl-based polymer and an additive, wherein the modified aromatic vinyl-based polymer is the modified aromatic according to any one of claims 1 to 3. Group V vinyl polymer C, the additive is filler D, and the composition condition is that the filler D is 3 to 100 parts by weight with respect to 100 parts by weight of the modified aromatic vinyl polymer C. A modified aromatic vinyl polymer composition, which is 300 parts by weight. 5. The thermoplastic resin E, wherein the additive has a functional group capable of reacting with an epoxy group, and the composition condition is 5 to 95% by weight of the modified aromatic vinyl polymer C. On the other hand, the modified aromatic vinyl polymer composition according to claim 4, wherein the thermoplastic resin E having a functional group capable of reacting with the epoxy group is 95 to 5% by weight. 6. The thermoplastic resin E having a functional group capable of reacting with the epoxy group is a polyester resin, a polyphenylene sulfide resin, a polycarbonate resin, a nylon resin, polyurethane, or a copolymer of ethylene and acrylic acid or an acrylic ester. 6. At least one resin selected from the group consisting of a combination, a polyolefin modified with an unsaturated carboxylic acid, a polystyrene modified with an unsaturated carboxylic acid, or another thermoplastic resin. Modified aromatic vinyl polymer composition. 7. A modified aromatic vinyl polymer composition comprising a modified aromatic vinyl polymer and an additive, wherein the modified aromatic vinyl polymer is the modified aromatic vinyl polymer composition according to claim 5. And the additive is the filler D, and the composition condition is 100 parts by weight of the modified aromatic vinyl polymer composition F, the filler D is 3 parts by weight.
~ 300 parts by weight of a modified aromatic vinyl polymer composition. 8. A modified aromatic vinyl polymer composition comprising a modified aromatic vinyl polymer and an additive, wherein the modified aromatic vinyl polymer is the modified aromatic vinyl polymer composition according to claim 6. G, the additive is the filler D, and the composition condition is 100 parts by weight of the modified aromatic vinyl polymer composition G, and the filler D is 3 parts by weight.
~ 300 parts by weight of a modified aromatic vinyl polymer composition. 9. A radical-generating agent H is further added to the aromatic vinyl polymer A and the epoxy group-containing acrylamide monomer B represented by the general formula (I) to obtain a reaction product in an extruder. The modified aromatic vinyl polymer according to claim 1, wherein 10. A modified aromatic vinyl-based polymer composition comprising a modified aromatic vinyl-based polymer and an additive,
The modified aromatic vinyl-based polymer is the modified aromatic vinyl-based polymer according to claim 9, the additive is a filler D, and the composition condition thereof is the aromatic vinyl-based polymer A. 0.01 to 20 parts by weight of the epoxy group-containing acrylamide monomer B and 100 to 100 parts by weight of the radical generator H.
Is 0 to 5 parts by weight and the filler D is 3 to 300 parts by weight, and the mixture is melt-kneaded to obtain a modified aromatic vinyl polymer composition. 11. An aromatic vinyl polymer A, a thermoplastic resin E having a functional group capable of reacting with an epoxy group, an epoxy group-containing acrylamide monomer B and a radical generator H.
In the modified aromatic vinyl polymer composition, the thermoplastic resin having a functional group capable of reacting with the epoxy group is 10 to 90% by weight of the aromatic vinyl polymer A. E is 90 to 10% by weight, and the A + E
0.1 to 10 parts by weight of the epoxy group-containing acrylamide monomer B and 0 to 10 parts by weight of the radical generator H per 100 parts by weight.
A modified aromatic vinyl polymer composition, characterized in that it is parts by weight and is melt-kneaded. 12. The thermoplastic resin E having a functional group capable of reacting with the epoxy group is a polyester resin, a polyphenylene sulfide resin, a polycarbonate resin, a nylon resin, a polyurethane, a copolymer of ethylene and acrylic acid or an acrylic acid ester. 12. The modified product according to claim 11, which is at least one resin selected from the group consisting of a combination, a polyolefin modified with an unsaturated carboxylic acid, a polystyrene modified with an unsaturated carboxylic acid, or another thermoplastic resin. Aromatic vinyl polymer composition. 13. A modified aromatic compound comprising an aromatic vinyl polymer A, a thermoplastic resin E having a functional group capable of reacting with an epoxy group, an epoxy group-containing acrylamide monomer B, a radical generator H and a filler D. In the vinyl polymer composition, the composition condition is that of the aromatic vinyl polymer A.
The thermoplastic resin E having a functional group capable of reacting with the epoxy group is 10 to 90% by weight, and the epoxy group-containing acrylamide unit amount is 100% by weight of the A + E. Modified aromatics characterized in that the body B is 0.1 to 10 parts by weight, the radical generator H is 0 to 10 parts by weight, and the filler D is 3 to 300 parts by weight, and these are melt-kneaded. Vinyl-based polymer composition. 14. The thermoplastic resin E having a functional group capable of reacting with the epoxy group is a polyester resin, a polyphenylene sulfide resin, a polycarbonate resin, a nylon resin, polyurethane, or a copolymer of ethylene and acrylic acid or an acrylic ester. Coupling, polyolefin modified with unsaturated carboxylic acids, polystyrene modified with unsaturated carboxylic acids or at least one resin selected from the group consisting of other thermoplastic resins, modified according to claim 13, characterized in that Aromatic vinyl polymer composition.