JPH0987464A - Polyamide resin composition for molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the polyamide resin composition comprising a polyamide resin, a graft-modified rubbery polymer and a plasticizer, exhibiting excellent heat resistance, good in flexibility, molded product surface, etc., and useful for automotive parts, etc. SOLUTION: This resin composition comprises (A) 100 pts.wt. of at least a polyamide resin selected from the group consisting of nylon 11, nylon 12 and nylon 6.12, (B) 1-100 pts.wt. of a graft-modified rubbery polymer produced by graft-copolymerizing (ii) 0.1-50 pts.wt. of a glycidyl group-having compound of the formula (Ar is a 6-23C aromatic hydrocarbon combined with at least a glycidyloxy group; R is H, methyl) and/or an unsaturated glycidyl ester and (iii) 0-500 pts.wt. of a vinylic monomer to (i) 100 pts.wt. of a rubbery polymer in the presence of (iv) a radical polymerization initiator in an amount of 0.001-100 pts.wt. per 100 pts.wt. of the total amount of the components (ii) and (iii), and (C) a plasticizer in an amount of 0-50 pts.wt. per 100 pts.wt. of the total amount of the components A and B.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyamide resin composition for molding which is excellent in heat resistance, flexibility and surface property of a molded product.

[0002]

2. Description of the Prior Art Polyamides such as nylon 11, nylon 12, and nylon 6 · 12 can be given arbitrary flexibility by mixing various plastic materials.
Chemical resistance such as oil resistance and salt water resistance, wear resistance, and excellent mechanical properties at low temperature, so it can be molded by various molding methods such as injection, extrusion, blow molding, for example, fuel line, oil tube, vacuum tube, It is used in a wide range of industrial fields such as automobiles, electricity, various machines, and sports equipment as parts for oil tanks, noise reduction gears, and sports equipment.

However, when these plasticized polyamides are used for a long period of time, the plasticizer bleeds out from the plasticized polyamide and the original properties are deteriorated.
Further, when exposed to a high temperature, for example, when exposed to an atmosphere of a temperature of 100 ° C. or higher, the plasticizer may volatilize from the plasticized polyamide and a crack may be generated in the molded product. If it's a big problem. Further, when a stabilizing formulation using a hindered phenol-based stabilizer, an aromatic amine-based stabilizer or a hindered amine-based stabilizer, which is widely used as a stabilizer for a normal polyamide, is applied to the plasticized polyamide, a plasticizer As the stabilizer volatilizes, the stabilizer also volatilizes, and there is a problem that the original stabilizer effect cannot be obtained.

[0004]

Therefore, an object of the present invention is to improve the heat resistance and to provide a polyamide resin composition for molding which is excellent in the balance of physical properties such as flexibility, surface property of molded product, oil resistance and mechanical properties. To provide.

[0005]

That is, the present invention relates to a molding polyamide resin composition comprising the following components (A), (B) and (C). . (A) Nylon 11, Nylon 12 and Nylon 6.1
100 parts by weight of at least one polyamide resin selected from the group consisting of 2, and (b) (a) with respect to 100 parts by weight of the rubbery polymer, (b)
General formula (I)

[0006]

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A glycidyl group represented by the formula (wherein Ar represents an aromatic hydrocarbon group having 6 to 23 carbon atoms bonded to at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). 0.1 to 50 parts by weight of a compound (b1) having a glycidyl group composed of an unsaturated glycidyl ester (b2), and (c) 0 to 500 parts by weight of a vinyl monomer, (b) 0.001 to 100 parts by weight of the total of the component and the component (c)
1 to 100 parts by weight of a graft-modified rubbery polymer obtained by polymerization in the presence of 10 parts by weight of (d) a radical initiator, and (C) a plasticizer, a total of 100 of the above-mentioned (A) component and (B) component.
0 to 50 parts by weight with respect to parts by weight.

Examples of the rubber polymer as the component (a) include ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, ethylene-propylene. -Diene copolymer, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyisoprene, polyisobutylene, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene- Examples thereof include isoprene block copolymers and ethylene-based ionomers, which may be used alone or in combination of two or more.

The compound (b1) having a glycidyl group, which is one of the components (b) for modifying the component (a), has the general formula (I)

[0010]

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(In the formula, Ar represents an aromatic hydrocarbon group having 6 to 23 carbon atoms bonded to at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) The compound having is derived from a modifier having at least one acrylamide group and at least one glycidyl group in the molecule. The acrylamide group includes a methacrylamide group in addition to the acrylamide group.

Such a compound is disclosed, for example, in JP-A-60 / 1985.
It can be manufactured by the method described in No. 130580. That is, it can be produced by condensing an aromatic hydrocarbon having at least one phenolic hydroxyl group in the presence of an N-methylolacrylamide or N-methylolmethacrylamide acid catalyst and then glycidylating the hydroxyl group with epihalohydrin. it can. As the aromatic hydrocarbon having at least one phenolic hydroxyl group, a phenolic compound having 6 to 23 carbon atoms is used. Specific examples of the phenolic compound include phenol, cresol, xylenol, carvacrol, thymol, naphthol, resorcin, hydroquinone, pyrogallol, phenanthrol and the like. Among them, 1 having an alkyl substituent
Polyhydric phenols are preferred. For example, when 2,6-xylenol and N-methylolacrylamide are used as starting materials, the structural formula (II)

[0013]

[Chemical 6]

A compound represented by can be obtained.

A compound (b) containing a glycidyl group represented by an unsaturated glycidyl ester, which is another one of the components (b) for modifying the component (a).
2) include glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of itaconic acid, mono-, di- and triglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endo-cis-bicyclo (2, 2, 1)
Examples thereof include mono- and diglycidyl esters of hept-5-ene-2,3-dicarboxylic acid, mono- and diglycidyl esters of allyl succinic acid, glycidyl esters of p-styrenecarboxylic acid, etc. These may be used alone or in combination of two or more. Used. Among these, glycidyl methacrylate is preferable from the viewpoints of cost and impregnation property into a rubbery polymer.

Examples of the vinyl monomer as the component (c) include styrene, which is an aromatic vinyl compound,
o-Methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, divinylbenzene, and other alkyl methacrylates having 1 to 22 carbon atoms, such as methyl methacrylate, ethyl methacrylate, and methacryl. Acid i-propyl, methacrylic acid n
-Butyl, t-butyl methacrylate, 2-methacrylic acid
Methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate, which are alkyl acrylates having an alkyl group having 1 to 22 carbon atoms, such as ethylhexyl and stearyl methacrylate. Vinyl methyl ether, which is a vinyl alkyl ether having an alkyl group having 1 to 22 carbon atoms, such as 2-ethylhexyl acrylate and stearyl acrylate.
Vinyl ethyl ether, vinyl n-propyl ether,
An unsaturated nitrile compound such as vinyl i-propyl ether, vinyl i-butyl ether, vinyl n-amyl ether, vinyl i-amyl ether, vinyl 2-ethylhexyl ether, vinyl octadecyl ether, etc.,
Unsaturated amide compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc., maleic acid di-alkyl esters, maleic acid di-n-amyl ester, maleic acid di-n-butyl ester, maleic acid diester -I-amyl ester, maleic acid di-i-butyl ester, maleic acid dimethyl ester, maleic acid di-n-propyl ester, maleic acid di-octyl ester, maleic acid dinonyl ester, etc. have 1 carbon atom in the alkyl group. ~ 8 allyl alkyl ethers, such as allyl ethyl ether and allyl n-octyl ether, and diene compounds such as dicyclopentadiene, butaene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, , 3-cyclohexadiene, 1,4
-Cyclohexadiene, 1,5-cyclohexadiene,
And 1,3-cyclooctadiene, and other vinyl monomers such as allyl methacrylate, acrylic acid, maleic acid methacrylic acid, maleic anhydride, and vinyl acetate. These may be used alone or in combination of two or more.

The radical initiator which is the component (d) is, for example, methyl ethyl ketone peroxide,
Di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl, 4-bis (t-butylperoxy) valerate, 2,5-dimethylhexane-2, 5-dihydroperoxide, α,
α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5
-Organic peroxides such as di (t-butylperoxy) hexyne-3 and benzoyl peroxide, or, for example, 1,1'-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano- 1-methylethyl)
Azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2, 2'-azobis (2,4
4-trimethylpentane), 2,2'-azobis (2-
Azo compounds such as acetoxypropane) and 2,2′-azobis (2-acetoxybutane) may be mentioned, and these may be used alone or in combination of two or more. Also,
These initiators can be appropriately selected as desired depending on various polymerization conditions such as polymerization method, polymerization temperature and time, or the molecular weight and viscosity of the resulting polymerized product.

Specific examples of the method for polymerizing the graft-modified rubbery polymer which is the component (B) of the present invention include:
An aqueous suspension containing the component (a), the component (b), the component (c), and the component (d) is prepared, and the component (b) and the component (c) in the aqueous suspension are mixed with the component (a). ) Impregnate the ingredients,
A method of polymerizing the component (b) and the component (c) can be mentioned. The ratio of the component (a), the component (b) and the component (c) in the aqueous suspension is 0.1 to 50 parts by weight, preferably 0, relative to 100 parts by weight of the component (a). .1
˜30 parts by weight, component (c) 0 to 500 parts by weight, preferably 0 to 200 parts by weight, more preferably 0 to 100 parts by weight, component (d) being the sum of components (b) and (c). The amount is 0.001 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight. When the proportion of the component (b) is higher than the above range, the fluidity is lowered and gelation is caused in some cases, and when the proportion is low, the thermal decomposition resistance and the adhesiveness are lowered. Further, when the ratio of the component (c) is higher than the above range, the polymerization of the vinyl-based monomers is predominant, so that excessive aggregation, fusion, or fusion in the aqueous suspension during polymerization,
Agglomeration occurs. Further, when the ratio of the component (d) is larger than the above range, the component (a) causes excessive crosslinking, and when it is small, the polymerization is insufficient.

Other polymerization methods for the (B) graft-modified rubbery polymer include (a) component, (b) component,
After mixing the components (c) and (d), the mixture is melted and kneaded by using a heating and kneading device such as an extruder,
Examples of the method include polymerizing the component (b) and the component (c) with respect to the component (a). In this case, component (a), (b)
The proportion of the component and the component (c) is 0.1 to 50 parts by weight, preferably 0.1 to 30 parts by weight, and the component (c) is 0 to 100 with respect to 100 parts by weight of the component (a). Parts by weight,
Preferably 0 to 50 parts by weight, the component (d) is added to the (b)
The total amount of the component and the component (c) is 0.
The amount is 001 to 10 parts by weight, preferably 0.05 to 5 parts by weight. When the ratio of the component (b) is higher than the above range,
If the amount is small, the fluidity is lowered and gelation is caused. If the amount is small, the thermal decomposition resistance and the adhesiveness are lowered. Further, when the ratio of the component (c) is higher than the above range, not only the excess vinyl-based monomer is distilled off and the addition effect is not improved, but also the mechanical properties are deteriorated and a foul odor may occur. is there. Further, when the ratio of the component (d) is larger than the above range,
If component (a) causes excessive crosslinking, and if it is too small, the polymerization will be insufficient.

The (B) graft-modified rubbery polymer of the present invention may be used in the form of a composition containing an unmodified rubbery polymer. In this case, the content of the unmodified rubbery polymer is 0 to 9
It is in the range of 5% by weight, preferably 0 to 80% by weight.

In the present invention, as the plasticizer which is the component (C) optionally used, p-oxybenzoic acid esters, aromatic oxycarboxylic acid ethers, phenols, aromatic oxyaldehydes, polyvalent Phenol phosphate esters, N-alkylbenzene sulfonamides, N-alkyl-p-toluene sulfonamides and the like can be mentioned. These may be used alone or in combination of two or more.

(A) Polyamide resin in the present invention,
The blending ratio of the (B) graft-modified rubbery polymer and the (C) plasticizer is (B) based on 100 parts by weight of the (A) component.
Component 1 to 100 parts by weight and component (C) are in the range of 0 to 50 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the total of components (A) and (B). If the compounding ratio is out of the above range, the balance of physical properties such as heat resistance, oil resistance, flexibility, and mechanical properties becomes insufficient.

The method for producing the polyamide resin composition for molding of the present invention is not particularly limited, and it is produced, for example, by uniformly mixing the respective components with a stirrer or the like and then melt-kneading. The method of melt kneading is not particularly limited, and may be melt kneading using a conventionally known blender such as an extruder, a heat roll, a Brabender, or a Banbury mixer.

If necessary, a stabilizer, an organic or inorganic filler, a catalyst for increasing the reactivity of the graft-modified rubbery polymer, etc. may be added to the molding polyamide resin composition of the present invention.

As the above-mentioned stabilizer, as an antioxidant,
For example, 2,4-bis (n-octylthio) -6- (4-
Hydroxy-3,5-di-t-butylanilino) -1,
3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di) -T-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4
Phenolic compounds such as 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and thioether compounds, or tetrakis (2,4-di-t)
-Butylphenyl) -4,4'-biphenylene phosphonite, tris (2,4-di-t-butylphenyl)
Phosphorite compounds such as phosphonite may be mentioned, and as the light stabilizer, dimethyl succinate-1- (2-
Hydroxyethyl) -4-hydroxy-2,2,6,6
-Tetramethylpiperidine polycondensate, poly [[6-
(1,1,3,3-tetramethylbutyl) imino-1,
3,5-triazine-2,4-diyl] [(2.2.
6.6-Tetramethyl-4-piperidyl) imino] hexamethylene [2,2,6,6-tetramethylpiperidyl) imino]], 2- (3,5-di-t-butyl-4-)
Examples thereof include hindered amine compounds such as hydroxybenzyl) 2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), which may be used alone or in combination of two or more. To be The amount of the stabilizer used is in the range of 0.01 to 20 parts by weight based on 100 parts by weight of the resin composition of the present invention. If it is less than the above range, the effect of adding the stabilizer is not sufficient, and if it is more than the above range, the mechanical properties are deteriorated.

As the filler, silica, talc,
Mica, glass fibers, glass beads, hollow glass beads, neutral clays, carbon fibers, aromatic polyamide fibers, aromatic polyester fibers, vinylon fibers, carbonized fibers, silicon carbide fibers, alumina fibers, potassium titanate fibers, and metals A fiber etc. are illustrated. These may be used alone or in combination of two or more.

The catalyst is not particularly limited, and is generally selected from compounds which promote the reaction of a carboxylic acid group, a hydroxyl group, an ester group and a glycidyl group, in one kind or in a combination of two or more kinds, but it is preferable. , Tertiary amines,
It is an amine compound such as a quaternary ammonium salt, a phosphonium salt, a phosphorus compound such as phosphine, or an imidazole. Of these, phosphorus compounds are particularly preferable from the viewpoint of heat resistance stability, and specifically, tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium chloride, tri-n-butylmethylphosphonium iodide. , Phosphonium salts such as tri-n-butylbenzylphosphonium chloride and tri-n-butylallylphosphonium bromide, and phosphines such as triphenylphosphine. The amount of the catalyst used is 100% by weight of the resin composition of the present invention.
0.001 to 2 parts by weight, preferably 0.
It is in the range of 005 to 1 part by weight. When it is less than the above range, the reaction promoting effect cannot be obtained, and when it is more than the above range, the mechanical properties are deteriorated.

Further, if necessary, the resin composition of the present invention contains a flame retardant, a pigment, an antistatic agent, a nucleating agent, or a thermoplastic crystalline material other than the present invention within a range not impairing the features of the present invention. A resin or an amorphous resin may be added.

[0029]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples, and can be changed as appropriate without departing from the scope of the invention. In the following description,
“Parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Reference Example 1: Graft-modified rubbery polymer (M
Production of ER1) In a pressure-resistant closed reaction tank, with respect to pure water 4200 parts, ethylene-vinyl acetate copolymer [Evaflex 260 (registered trademark) manufactured by Mitsui DuPont Polychemical Co., Ltd .: vinyl acetate content 28%, melt flow) Rate 6g / 10
Min] 1400 parts, styrene 300 parts, N- [4- (2,
3-Epoxypropoxy) -3,5-dimethylbenzyl] acrylamide 200 parts, glycidyl methacrylate 100 parts, 1,1-bis (t-butylperoxy)
6.0 parts of 3,3,5-trimethylcyclohexane, 30 parts of tribasic calcium phosphate, and 1.0 part of an emulsifier [Latemuru PS (registered trademark) manufactured by Kao Co., Ltd.] were mixed and stirred to form an aqueous suspension. Obtained. The aqueous solution was stirred at 100 ° C. for 1 hour and then at 110 ° C. for 3 hours to complete the polymerization. The obtained particles were washed with water to remove tricalcium phosphate and latemur PS, and then dried to obtain a graft-modified rubbery polymer (MER1).

Reference Example 2: Graft-modified rubbery polymer (M
Production of ER2) In a pressure-resistant closed reaction tank, with respect to 4200 parts of pure water, ethylene-ethyl acrylate copolymer [Evaflex EEAA-70 manufactured by Mitsui DuPont Polychemical Co., Ltd.
3 (registered trademark): ethyl acrylate content 25%, melt flow rate 5 g / 10 min] 1400 parts, styrene 4
00 parts, N- [4- (2,3-epoxypropoxy)-
3,5-dimethylbenzyl] acrylamide 200 parts,
1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 6.0 parts, tricalcium phosphate 30 parts, and an emulsifier [Latemuru PS manufactured by Kao Corporation]
(Registered trademark)] (1.0 part) was mixed and mixed with stirring to obtain an aqueous suspension. After stirring the aqueous solution at 100 ° C. for 1 hour,
Further, the mixture was stirred at 110 ° C. for 3 hours to complete the polymerization. The obtained particles were washed with water to remove tricalcium phosphate and latemur PS, and then dried to obtain a graft-modified rubbery polymer (MER2).

Reference Example 3: Graft-modified rubbery polymer (M
Production of ER3) In a pressure tightly closed reaction tank, with respect to 4200 parts of pure water, an ethylene-propylene copolymer [EP0 manufactured by JSR Corporation
2P (registered trademark): propylene content 26%, melt flow rate 3.2 g / 10 minutes] 1600 parts, methyl methacrylate 200 parts, styrene 100 parts, glycidyl methacrylate 100 parts, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 4.0
Parts, 30 parts of tribasic calcium phosphate, and 1.0 part of an emulsifier [Latemuru PS (registered trademark) manufactured by Kao Corporation) were mixed and stirred to obtain an aqueous suspension. 100 parts of the aqueous solution
After stirring at 0 ° C for 1 hour, the mixture was further stirred at 110 ° C for 3 hours to complete the polymerization. The obtained particles were washed with water to remove tricalcium phosphate and latemur PS, and then dried to obtain a graft rubber polymer (MER3).

Reference Example 4: Graft-modified rubbery polymer (M
ER4) Production of ethylene-vinyl acetate copolymer [Eva Flex 260 (registered trademark) manufactured by Mitsui DuPont Polychemical Co., Ltd .:
Vinyl acetate content 28%, melt flow rate 6g / 10
Min] 100 parts, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide 15
Parts, and 0.23 parts of n-butyl-4,4-bis (t-butylperoxy) valerate were dry-blended and then charged into a twin-screw extruder at a rate of 15 kg / h and melted at a cylinder temperature of 190 ° C. Kneaded and pelletized. The pellets were dried at 50 ° C. for 12 hours to obtain a graft-modified rubbery polymer (MER4).

Examples 1 to 6 Each component of the resin composition of the present invention, (A) polyamide resin,
A resin composition was produced by using the following components as the (B) graft-modified rubbery polymer and the (C) plasticizer, with the combinations of components and the mixing ratios shown in Table 1. (A) Polyamide resin: Nylon 12 (manufactured by Daicel Hüls Ltd., abbreviated as Ny12 in the table) (B) Graft-modified rubbery polymer: Graft-modified rubbery polymer produced in Examples 1 to 4 (MER1 to MER1) MER4) (C) Plasticizer: 2-ethylhexyl-p-hydroxybenzoate

The resin composition and the test piece were manufactured by the following methods. First, each component in the ratio shown in Table 1 was added to 2 mm of 45 mm.
It was melt-kneaded and pelletized at a cylinder temperature of 250 ° C. by a shaft extruder. The pellet was vacuum dried to obtain a desired resin composition. The dried pellets were hot-pressed to produce a 2 mm thick press sheet.

The evaluation method was carried out by the following items and methods, and the results are shown in Table 1. (1) Flexibility: A test piece was punched out from the press sheet, and A
The flexural modulus was measured according to STM D790. (2) Heat resistance: Using a test piece similar to the test piece for evaluating the flexural modulus, the flexural modulus before heating of the flexural modulus of the test piece that was heat-treated at 150 ° C. for 200 hours in a hot air oven (%) And the presence or absence of cracks on the surface of the test piece. The flexural modulus is measured by ASTM
The retention rate was calculated according to D790 using the following calculation formula. [(Elastic modulus before heating) / (Elastic modulus after heating)] × 100 (%) Further, the presence or absence of cracks was visually determined. (3) Molded product surface property Visual evaluation was performed in three levels according to the following criteria. ◯: The surface of the press sheet is smooth and glossy. Δ: The glossiness of the press sheet surface is slightly lacking. X: Mattes are seen on the surface of the press sheet, and the surface is matte.

Comparative Examples 1 and 2 A resin composition and a test piece were prepared in the same manner as in Example except that the graft-modified rubbery polymer was not used, and the same property evaluation as in Example was carried out. Table 1 shows the blending ratio of each component and the characteristic evaluation results.

Comparative Example 3 The ethylene-ethyl acrylate copolymer used in Reference Example 2 was used in place of the graft-modified rubbery polymer (EE in the table).
A resin composition and a test piece were prepared in the same manner as in the example except that (abbreviated as A) was used, and the same characteristic evaluation as in the example was performed. Table 1 shows the blending ratio of each component and the result of characteristic evaluation.

Comparative Example 4 Implementation was carried out except that an ethylene-glycidyl methacrylate copolymer [Sumitomo Chemical Co., Ltd., Bondfast E (registered trademark), abbreviated as BF in the table] was used in place of the graft-modified rubbery polymer. A resin composition and a test piece were prepared in the same manner as in the example, and the same characteristic evaluation as in the example was performed. Table 1 shows the blending ratio of each component and the result of characteristic evaluation.

[0040]

[Table 1]

[0041]

As described above, a molding polyamide resin resin comprising the (A) polyamide resin of the present invention, the (B) graft-modified rubbery polymer of the present invention, and (C) a plasticizer optionally added. The composition exhibits excellent heat resistance, flexibility, and good surface properties of the molded product. For example, it is possible to obtain a molded product suitable for various automobile parts, mechanical parts, electric / electronic parts, sports parts, etc. Is.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Kenji Kurimoto 2-9-30-12 Maikodai, Tarumi-ku, Kobe-shi, Hyogo

Claims (8)

[Claims] 1. A molding polyamide resin composition comprising the following components (A), (B) and (C): (A) Nylon 11, Nylon 12 and Nylon 6.1
100 parts by weight of at least one polyamide resin selected from the group consisting of (B) (a) rubber polymer, and (b)
General formula (I) (Wherein, Ar represents an aromatic hydrocarbon group having 6 to 23 carbon atoms bonded to at least one glycidyloxy group;
Represents a hydrogen atom or a methyl group. ) 0.1 to 50 parts by weight of a compound (b1) having a glycidyl group and / or a compound (b2) having a glycidyl group composed of an unsaturated glycidyl ester, and (c) a vinyl monomer 0 to 500 Graft modified rubbery polymer 1 obtained by polymerizing 1 part by weight in the presence of 0.001 to 100 parts by weight of (d) radical initiator with respect to 100 parts by weight of the total of components (b) and (c). To 100 parts by weight, and (C) plasticizer, a total of 100 of the above components (A) and (B).
0 to 50 parts by weight with respect to parts by weight. 2. The rubbery polymer as the component (a) is an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer,
Ethylene-propylene copolymer, ethylene-propylene-diene copolymer, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyisoprene, polyisobutylene, styrene-butadiene block copolymer, hydrogenated styrene- The molding polyamide resin composition according to claim 1, which is at least one selected from the group consisting of a butadiene block copolymer, a hydrogenated styrene-isoprene block copolymer, and an ethylene ionomer. 3. The glycidyl group-containing compound (b1) as the component (b) has the structural formula (II): The polyamide resin composition for molding according to claim 1 or 2, represented by 4. The molding polyamide resin composition according to claim 1, wherein the compound (b2) having a glycidyl group consisting of the unsaturated glycidyl ester as the component (b) is glycidyl methacrylate. 5. The component (b) has the structural formula (II): The polyamide resin composition for molding according to claim 1 or 2, which is a mixture of 1 to 99% by weight of the compound represented by and 99 to 1% by weight of glycidyl methacrylate. 6. The vinyl monomer as the component (c) is an aromatic vinyl compound, an alkyl acrylate having an alkyl group having 1 to 22 carbon atoms, or an alkyl group having 1 to 12 carbon atoms.
Methacrylic acid alkyl ester having 22 carbon atoms, vinyl alkyl ether having 1 to 22 carbon atoms in alkyl group, vinyl alcohol, unsaturated nitrile compound, unsaturated amino compound, dialkyl maleate having 1 to 9 carbon atoms in alkyl group At least one selected from the group consisting of an ester, an allyl alkyl ether having an alkyl group having 1 to 8 carbon atoms, an allyl acrylic ester, a diene compound, maleic anhydride, maleic acid, acrylic acid, methacrylic acid, and vinyl acetate. Item 1. A polyamide resin composition for molding according to items 1 to 5. 7. A method for producing a graft-modified rubbery polymer as the component (B) comprises: 100 parts by weight of the component (a), 0.1 to 50 parts by weight of the component (b), and 0 to 500 parts by weight of the component (c). Department,
And the total of the component (d) and the component (b) and the component (c) is 1
An aqueous suspension containing 0.001 to 10 parts by weight with respect to 00 parts by weight was prepared, and component (a) was impregnated with the components (b) and (c) in the aqueous suspension, and (b) 7. The polyamide resin composition for molding according to claim 1, which is a method of polymerizing the component) and the component (c). 8. A method for producing a graft-modified rubbery polymer as the component (B) comprises: 100 parts by weight of the component (a), 0.1 to 50 parts by weight of the component (b), and 0 to 100 parts of the component (c). Parts, and 0.001 to 10 parts by weight of the component (d) with respect to 100 parts by weight of the total of the components (b) and (c) are melt-kneaded, and the component (b) is added to the component (a). And a method for polymerizing the component (c), wherein the polyamide-based resin composition for molding according to claims 1 to 6.