JP3221905B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having improved impact resistance of a thermoplastic polyamide resin .

[0002]

2. Description of the Related Art Thermoplastic polyamide resins are rigid and mechanical.
Although it has excellent mechanical strength and is expected to be used in a wide range of applications as an engineering plastic, its application is limited due to poor impact resistance.

A number of proposals have been made for improving the impact resistance of polyamide resins. For example, US Pat.
Nos. 4,174,358 and 4,536,541 disclose polyamide-modified acid-modified ethylene / propylene copolymers (acid-modified EP).
A method of blending R) has been proposed.

[0004]

However , according to the methods described in U.S. Pat. Nos. 4,174,358 and 4,536,541, the impact strength at low temperatures cannot be said to be sufficiently high. There is a need for compositions that exhibit better impact resistance in the temperature range .

[0005]

In view of such circumstances, the present inventors have made intensive studies to further improve the impact resistance of a thermoplastic polyamide resin , and as a result, specific thermoplastic resins have been identified. The present inventors have found that the impact resistance can be improved over a wide temperature range by blending the graft copolymer and the organosilane compound containing an epoxy group, and have reached the present invention.

That is, the gist of the present invention is a thermoplastic polyamide.
Resin (A) 60 to 99 parts by weight, a polyorganosiloxane rubber or a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are entangled with each other so that they cannot be separated from each other. A silane compound (C) having an epoxy group is present in an amount of 1 to 40 parts by weight of a graft copolymer (B) obtained by graft-polymerizing a monomer and 100 parts by weight of a total of both components (A) and (B). 0.11 to 10 parts by weight of the resin composition.
The resin composition contains 10 to 300 parts by weight of a filler based on parts by weight.

The thermoplastic polyamide tree used in the present invention
Examples of the fats include polyamides obtained from aliphatic, aromatic or alicyclic dicarboxylic acids and diamines, and polyamides obtained from aminocarboxylic acids and lactams. Specific examples of such polyamides include 6-nylon, 12-nylon, 6,6-nylon, 4,6-nylon.
Nylon, nylon MXD6, 6-nylon and 6,6-
Examples thereof include a copolymer of nylon and a copolymer of 6-nylon and 10-nylon. Of these, 6-
Nylon, 6,6-nylon and 4,6-nylon are preferably used.

The polyorganosiloxane rubber component used in the present invention comprises an organosiloxane, a cross-linking agent for polyorganosiloxane rubber (hereinafter referred to as cross-linking agent (I)), and a graft-crossing agent for polyorganosiloxane rubber (hereinafter referred to as graft-crossing agent (I)). ) Can be obtained as fine particles obtained by polymerizing the above.

Examples of the organosiloxane include cyclic organosiloxanes having three or more membered rings, and those having a three to six membered ring are preferably used. Hexamethylcyclotrisiloxane as specific examples of preferred cyclic organosiloxanes,
Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane,
Tetramethyltetraphenylcyclotetrasiloxane,
Octaphenylcyclotetrasiloxane and the like can be exemplified,
These may be used alone or as a mixture of two or more.
The amount of the cyclic organosiloxane used is preferably 60% by weight or more in the polyorganosiloxane rubber.
It is more preferable that the content be not less than% by weight.

As the crosslinking agent (I), a trifunctional or tetrafunctional silane-based crosslinking agent, that is, a silane compound having three or four alkoxy groups is used. Specific examples thereof include trimethoxymethylsilane and triethoxy. Examples thereof include phenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. The crosslinking agent (I) is preferably a tetrafunctional one, and among the tetrafunctional crosslinking agents, tetraethoxysilane is particularly preferred.

The amount of the crosslinking agent (I) used is preferably from 0.1 to 30% by weight, more preferably from 0.5 to 10% by weight in the polyorganosiloxane rubber. If the amount of the crosslinking agent (I) is less than 0.1% by weight, the impact strength of a molded article from the composition becomes low, and the appearance of the molded article tends to deteriorate. Further, if it is used in an amount exceeding 30% by weight, it does not contribute to the formation of a further crosslinked structure.

The graft-crosslinking agent is a monomer having two or more polymerizable unsaturated groups having different reactivities, and one of the polymerizable unsaturated groups is polymerized together with a polymerizable component at the time of polymerization and incorporated into rubber. However, the other polymerizable unsaturated group is a monomer which remains without reacting and is polymerized together with the graft branch constituent during the subsequent graft polymerization. Examples of the graft crosslinking agent (I) include compounds having an alkoxysilyl group and a vinyl group or a mercapto group. The siloxane group is involved in the polymerization and is incorporated into the polyorganosiloxane rubber. It does not react at this time but reacts during the subsequent graft polymerization or the polymerization of the poly (meth) acrylate rubber in the presence of the polyorganosiloxane rubber during the production of the composite rubber.

Specific examples thereof include a compound capable of forming a unit represented by the following formula.

[0014]

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In each formula, R ¹ represents a methyl group, an ethyl group, a propyl group or a phenyl group, R ² represents a hydrogen atom or a methyl group, n represents 0, 1 or 2, and p represents an integer of 1 to 6. .

Among these, (meth) acryloyloxysilane, which can form a unit of the formula (I-1), has a high grafting efficiency and can form an effective graft chain, and exhibits impact resistance. Is advantageous. Note that the formula (I-
Methacryloyloxysilane is particularly preferable as a unit capable of forming the unit 1).

Examples of the unit capable of forming the unit of the formula (I-2) include vinyltrimethoxysilane and vinylmethyldimethoxysilane. Examples of the unit capable of forming the unit of the formula (I-3) include 4-vinylphenyldimethoxymethylsilane and 4-vinylphenyltrimethoxysilane. Those which can form the unit of the formula (I-4) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane.
Mercaptopropyldiethoxyethylsilane and the like can be exemplified.

Specific examples of methacryloyloxysilane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane. Methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane, and the like. Among these, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrisilane Methoxysilane can be mentioned as a more preferable one. The amount of the grafting agent (I) to be used is 0.1 to 10% by weight, preferably 0.1 to 5% by weight in the polyorganosiloxane rubber.

The polyorganosiloxane rubber can be obtained as a latex by the method described in, for example, US Pat. Nos. 2,289,1920 and 3,247,725. In the present invention, for example, a mixed solution containing an organosiloxane, a crosslinking agent (I), and a graft crossing agent (I) is mixed with a homogenizer or the like in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid. It is preferred to produce the polyorganosiloxane rubber by a method of shear-mixing with water using

Alkyl benzene sulfonic acid is preferred because it functions as an emulsifier for the organosiloxane and also serves as a polymerization initiator. In this case, it is preferable to use an alkylbenzene sulfonic acid in combination with a metal salt of an alkylbenzene sulfonic acid, a metal salt of an alkyl sulfonic acid, or the like, since this is effective for stably maintaining the polymer during graft polymerization.

The termination of the polymerization can be carried out by neutralizing the latex with an aqueous alkali solution such as sodium hydroxide, potassium hydroxide or sodium carbonate.

The composite rubber is obtained by adding an alkyl (meth) acrylate to the polyorganosiloxane rubber latex obtained above,
Crosslinking agent for polyalkyl (meth) acrylate rubber (hereinafter referred to as crosslinking agent (II)) and graft crossing agent for polyalkyl (meth) acrylate rubber (hereinafter graft crossing agent (I
(I)), impregnating these components into polyorganosiloxane rubber particles, and then polymerizing.

When a composite rubber is used as the rubber component, the graft-crosslinking agent (I) is not always necessary when producing the polyorganosiloxane rubber latex. That is, when the graft component is graft-polymerized to the polyorganosiloxane rubber, the graft polymerization becomes difficult unless the rubber contains the graft-crosslinking agent (I). In the case of the composite rubber, the graft-crosslinking agent (I) is used. Even if it is not used, the polyorganosiloxane rubber particles are impregnated with polyalkyl (meth) acrylate rubber monomers in order to polymerize these monomers in order to polymerize these monomers. The polyalkyl (meth) acrylate rubber has a structure in which the two components cannot be separated from each other in a state where they are intertwined with each other, and the graft cross-linking agent (II) is contained in the polyalkyl (meth) acrylate rubber component. Therefore, graft polymerization to the composite rubber becomes possible.

Alkyl (meth) used for preparation of composite rubber
Examples of the acrylate include linear or branched alkyl acrylates having an alkyl group having 1 to 8 carbon atoms and alkyl methacrylates having an alkyl group having 6 to 12 carbon atoms. Specific examples of these include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, 3-pentyl acrylate, hexyl acrylate, n-heptyl acrylate, 2-heptyl acrylate, n-octyl acrylate, 2-
Octyl acrylate, 2-ethylhexyl acryle
Hexyl methacrylate, octyl methacrylate, decyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, etc., of which n-butyl acrylate is preferred. it can.

As the crosslinking agent (II), (meth) acrylates having two or more polymerizable unsaturated bonds are used, and specific examples are ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3- Butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and the like can be exemplified.

The graft-linking agent (II) is polymerized together with other components during the polymerization for producing the polyalkyl (meth) acrylate rubber and incorporated into the rubber. At that time, at least a part of the polymerizable unsaturated groups reacts. Monomer having two or more polymerizable unsaturated groups having different reactivities so that the remaining unsaturated group can be polymerized together with the graft branch constituent at the time of subsequent graft polymerization. Methacrylate, triallyl cyanurate
And triallyl isocyanurate.

In the case of allyl methacrylate, a part of the more reactive unsaturated group reacts during the polymerization of the polyalkyl (meth) acrylate rubber to form a cross-linking bond, and the remaining unsaturated group forms Since it reacts during graft polymerization to form a graft bond, it functions as both a crosslinking agent (II) and a graft crossing agent (II).

Each of the crosslinking agent (II) and the graft-linking agent (II) may be a single component, or two or more components may be used in combination. The amount of the crosslinking agent (II) and the amount of the grafting agent (II) used are respectively polyalkyl (meth)
It is 0.1 to 10% by weight in the acrylate rubber component, and when only the allyl methacrylate is used as the crosslinking agent (II) and the graft crossing agent (II), it may be used in an amount of 0.2 to 20% by weight.

The polymerization of the polyalkyl (meth) acrylate rubber component is carried out by adding the above alkyl (meth) acrylate into a latex of a polyorganosiloxane rubber neutralized by adding an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate. ) An acrylate, a cross-linking agent (II) and a graft cross-linking agent (II) may be added to impregnate the polyorganosiloxane rubber particles, and then an ordinary radical polymerization initiator may be used. As the polymerization proceeds, a crosslinked network of polyalkyl (meth) acrylate rubber is formed which is entangled with the crosslinked network of polyorganosiloxane rubber, and the polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber which cannot be separated substantially. A latex of a composite rubber comprising the components is obtained.

The composite rubber preferably has a gel content of 80% or more as measured by extraction with toluene at 90 ° C. for 4 hours.

In the composite rubber, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the main skeleton of the polyalkyl (meth) acrylate rubber component is a repeating unit derived from n-butyl acrylate. It is preferable to have.

The ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component in the composite rubber is preferably 1% by weight or more for the former and 99% by weight or less for the latter, and 5% by weight or more for the former. More preferably, the latter is 95% by weight or less. If the content of the polyorganosiloxane rubber component is less than 1% by weight, the impact resistance, particularly the low-temperature impact resistance, becomes insufficient.

The polyorganosiloxane-based graft copolymer used in the present invention (hereinafter simply referred to as "graft copolymer") is obtained by graft-polymerizing a vinyl monomer onto the polyorganosiloxane rubber or composite rubber thus obtained. Can be obtained.

The vinyl monomers used for the graft polymerization include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; methyl methacrylate;
Methacrylates such as -ethylhexyl methacrylate; acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; and various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. Are used alone or in combination of two or more. Among these vinyl monomers, (meth) acrylates are preferred, and among them, methyl methacrylate is particularly preferred.

The amount of the vinyl monomer in the graft copolymer is 1% based on the weight of the graft copolymer.
It is preferably from 60 to 60% by weight, more preferably from 5 to 40% by weight. If the amount of the vinyl monomer is less than 1% by weight, the compatibility between the graft copolymer and the thermoplastic polyamide resin tends to be insufficient, and the expression of impact resistance tends to be insufficient. , The effect of imparting impact resistance tends to decrease.

The above vinyl monomer is added to a polyorganosiloxane rubber or a composite rubber latex, and polymerized in a single step or in multiple steps by a radical polymerization technique. The graft copolymer latex thus obtained is subjected to the polymerization of calcium chloride, magnesium sulfate or the like. The graft copolymer used in the present invention can be separated and recovered by throwing it into hot water in which a metal salt is dissolved, salting out and coagulating.

When the average particle size of the graft copolymer used in the present invention is less than 0.08 μm, the resulting resin composition tends to have insufficient impact resistance. Since the impact strength tends to be insufficient and the surface appearance of a molded article made from the resin composition tends to deteriorate, the average particle size is 0.08 to 0.6 μm.
m is preferably in the range. In order to obtain a graft copolymer having such an average particle diameter, it is preferable to produce the polyorganosiloxane rubber or composite rubber used by emulsion polymerization.

As the organosilane compound having an epoxy group used in the present invention, one or a mixture of two or more compounds represented by the following formulas can be mentioned.

[0039]

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In the above formula, n is an integer of 1 to 3;
⁵ is a methyl group or an ethyl group, and Y and Z are groups selected from the following groups.

[0041]

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In the above formula, R ⁶ represents an alkylene group having 1 to 3 carbon atoms, R ⁷ represents a single bond or an alkylene group having 1 to 3 carbon atoms, and R ⁸ represents a methyl group or an ethyl group.

Among the above-mentioned organosilane compounds having an epoxy group, glycidoxyalkyl trialkoxysilane, glycidoxyalkylalkyldialkoxysilane, (3,4-epoxycyclohexylalkyltrialkoxysilane) and the like can be exemplified as preferable ones. Specific examples of these compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

The resin composition of the present invention is a thermoplastic polyamide
Resin (A) 60 to 99 parts by weight, graft copolymer (B)
1 to 40 parts by weight, and a total of 1 of both components (A) and (B)
The resin composition contains 0.01 to 10 parts by weight of a silane compound having an epoxy group (C) based on 00 parts by weight.

If the amount of the component (B) is less than 1 part by weight, the development of impact strength becomes insufficient, and if it exceeds 40 parts by weight, the heat resistance of the composition is undesirably reduced. Further, if the amount of the component (C) is less than 0.01 part by weight based on 100 parts by weight of the total of both the components (A) and (B), the manifestation of impact strength is insufficient and the content exceeds 10 parts by weight. And the fluidity is lowered.

As long as the resin component is as described above, the composition of the present invention may further contain a filler if necessary. As the filler, fibrous, particulate, powdery or other various shapes can be used, and as such a filler, glass fiber, carbon fiber, potassium titanate,
Asbestos, silicon carbide, ceramic fiber, metal fiber, silicon nitride, aramid fiber, barium sulfate, calcium sulfate, calcium silicate, calcium carbonate, magnesium carbonate, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, disulfide Molybdenum, mica, talc, kaolin, pyrophyllite, bentonite, sericite, zeolite, wollastonite, ferrite,
Examples include graphite, gypsum, glass beads, glass balloons, quartz and the like.

When a filler is blended, 10 parts of the filler is added to 100 parts by weight of the total of the components (A), (B) and (C).
To 300 parts by weight. If the amount is less than 10 parts by weight, the effect of improving the heat resistance and mechanical strength by the blending of the filler is small,
If the amount exceeds 300 parts by weight, the melt fluidity of the composition is undesirably reduced.

The resin composition of the present invention comprises a thermoplastic polyamide.
Although a silane compound having a de resin and the graft copolymer and the epoxy group may be prepared by any means as long as it is obtained by melt-mixing a thermoplastic polyamide resin graft copolymers in the dry state It is preferable to melt-knead the mixture with an organic silane compound having an epoxy group or a filler and form a pellet in an extruder.

[0049]

The present invention will be described in detail with reference to the following examples. In the following description, “parts” means parts by weight. In addition, the measuring method of various physical properties in each Example and Comparative Example is based on the following method. Average particle diameter: A latex diluted with water is used as a sample liquid, and a quasi-elastic light scattering method (MALVERN SYSTEM 4600,
Measurement temperature 25 ° C., measured by the scattering angle 90 ^0). Izod impact strength: According to the method of ASTM D-256 (with a 1/8 "notch), but performed under absolutely dry conditions. Thermal deformation temperature: By the method of ASTM D-256 (load: 18.6 kg / cm2). : The surface of the injection-molded article was visually judged, and the good one was evaluated as ○, the poor one as ×, and the poor one as △. Coating adhesion: A flat plate was molded and an acrylic urethane paint (toluene A reaction product of diisocyanate and acrylic polyol) is applied, dried and dried at 1 mm intervals.
One cut was made to make 100 grids, a cellophane adhesive tape was stuck on the grid, and the number of peeled coatings when peeling the tape in the vertical direction was evaluated. That is, when the number of peeled coating films is 10 or less, ◎, 11
In the case of 20 sheets, ○ was indicated in the case of 21 to 40 sheets, and in the case of 41 or more sheets, the mark was ×.

Reference Example 1 Production of polyorganosiloxane-based graft copolymer S-1: 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane were mixed. Thus, 100 parts of a siloxane mixture was obtained. 200 parts of distilled water prepared by dissolving 1 part of dodecylbenzenesulfonic acid and 1 part of sodium dodecylbenzenesulfonate was added, and 100 parts of the siloxane mixture was added thereto.
After preliminary stirring at 000 rpm, the mixture was homogenized by a homogenizer.
Emulsification was performed under a pressure of 00 kg / cm ² to obtain an organosiloxane latex. This latex was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours while stirring and mixing, and then left at 20 ° C. for 48 hours, and then the pH of the latex was adjusted with an aqueous sodium hydroxide solution. After neutralization to 7.0, a polyorganosiloxane rubber latex (hereinafter referred to as PDMS-1) was obtained. The conversion to the obtained polyorganosiloxane rubber was 89.7%, and the average particle size of the polyorganosiloxane rubber was 0.8%.
It was 16 μm.

33 parts of this PDMS-1 was collected and placed in a separable flask equipped with a stirrer, 267 parts of distilled water was added, the atmosphere was replaced with nitrogen, the temperature was raised to 50 ° C., and n-butyl acrylate 80 was added. , A mixture of 1.6 parts of allyl methacrylate and 0.192 parts of ter-butyl hydroperoxide was charged and stirred for 30 minutes, and the mixture was permeated into the polyorganosiloxane rubber particles. Then, ferrous sulfate 0.001 part, ethylenediaminetetraacetic acid disodium salt 0.003 part, Rongalit 0.24 part and distilled water 10
Parts of the mixed solution were charged to start radical polymerization, and then kept at an internal temperature of 70 ° C. for 2 hours to obtain a composite rubber latex. A part of this latex was collected and dried to obtain a solid, which was extracted with toluene at 90 ° C. for 4 hours, and the gel content was measured to be 95.3% by weight.

A mixed solution of 10 parts of methyl methacrylate and 0.024 part of tert-butyl hydroperoxide was added to the composite rubber latex, and the mixture was kept at an internal temperature of 70 ° C. for 4 hours to perform graft polymerization on the composite rubber. The conversion of methyl methacrylate was 97.5%, and the average particle size of the graft copolymer latex was 0.20 μm.
The obtained graft copolymer latex was dropped into 600 parts by weight of hot water containing 1.5% by weight of calcium chloride, coagulated and separated, washed repeatedly with water, and dried at 80 ° C. for 24 hours to obtain a polyorganosiloxane. -Based graft copolymer S-
97.7 parts by weight of the dried powder 1 was obtained.

Reference Examples 2 to 8 Polyorganosiloxane-based graft copolymers S-2 to S
Production of -8: The amount of PDMS-1 collected, the amount of distilled water added, and the amounts of n-butyl acrylate and allyl methacrylate added in the composite rubber polymerization are as shown in Table 1 (Reference Examples 2 to 7).
Or subjected to graft polymerization in the PDMS-1 without producing a composite rubber (Example 8), and the amount of methyl methacrylate in the graft-polymerized with as described in Table 1 following
Except for the above, a polyorganosiloxane-based graft copolymer was obtained in the same manner as in Reference Example 1 . Table 1 shows the polymerization rate of methyl methacrylate, the average particle size of the graft copolymer, and the yield.

[0054]

[Table 1]

REFERENCE EXAMPLE 9 A polyorganosiloxane graft copolymer S-9 was obtained in the same manner as in Reference Example 1, except that the siloxane mixture was a mixture of 2 parts of tetraethoxysilane and 98 parts of octamethylcyclotetrasiloxane. . The gel content of the composite rubber is 97%, the polymerization rate of methyl methacrylate is 98.1%,
The average particle size of the graft copolymer was 0.21 μm.

Reference Example 10 A polyorganosiloxane-based graft copolymer S-10 was prepared in the same manner as in Reference Example 1 except that the same amount of 2-ethylhexyl acrylate was used instead of n-butyl acrylate.
I got The gel content of the composite rubber was 98%, the conversion of methyl methacrylate was 97.2%, and the average particle size of the graft copolymer was 0.21 μm.

Reference Example 11 A polyorganosiloxane-based graft copolymer S-11 was obtained in the same manner as in Reference Example 1, except that the same amount of styrene was used instead of methyl methacrylate. The gel content of the composite rubber is 98%, and the polymerization rate of methyl methacrylate is 97.6.
%, The average particle size of the graft copolymer was 0.20 μm.

Examples 1 to 20 and Comparative Examples 1 to 7 As the thermoplastic polyamide, 6-nylon (UBE6 nylon 1013NW8, manufactured by Ube Industries, Ltd.), 6,
6-nylon (Ube Industries, Ltd., UBE66 nylon 2020B), 4,6-nylon (Unitika Ltd.)
Manufactured by Unitika Nylon 46 F5000), and the polyorganosiloxane-based graft copolymers S-1 to S-8 obtained in each Reference Example and the organic silane compound having an epoxy group shown in Table 2 are shown in Table 2. The mixture was blended at the ratios shown, melt-kneaded at a cylinder temperature of 260 to 290 ° C. using a twin-screw extruder (TEM-35B, manufactured by Toshiba Machine Co., Ltd.), and pelletized.

After the obtained pellets were dried, a test piece was molded at a cylinder temperature of 260 to 290 ° C. and a mold temperature of 70 ° C. using an injection molding machine (Promat injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.) and subjected to impact resistance. The sex was evaluated.

For comparison, in the case of only polyamide,
Evaluation was also made of the case where the graft copolymer or the organic silane having an epoxy group was not blended, and the case where an organic silane compound having another functional group was used instead of the silane compound having an epoxy group. Table 2 shows the results.
And Table 3.

In Table 2 and the following tables, the organic silane compounds are as follows. (a): γ-glycidoxypropyltrimethoxysilane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) (b): γ-glycidoxypropylmethyldiethoxysilane (KBE402, manufactured by Shin-Etsu Chemical Co., Ltd.) c): β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM30)
3) (d): γ-mercaptopropyltrimethoxysilane (KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) (e): γ-aminopropyltriethoxysilane (KBE903, manufactured by Shin-Etsu Chemical Co., Ltd.) And in the following table, 66, 6, and 46 in the section of polyamide represent 6,6-nylon, 6-nylon, and 4,6-nylon, respectively.

[0062]

[Table 2]

[0063]

[Table 3]

Examples 21 to 28 and Comparative Examples 8 to 13 Glass fiber (GF), carbon fiber (CF),
As an example of blending talc (TA), a test piece was injection molded and evaluated in the same manner as in Example 1 except that the blending ratio shown in Table 4 was used. Table 4 shows the results.

[Table 4]

[0065]

The resin composition of the present invention has excellent impact resistance especially at low temperatures, and can be used under more severe conditions than before. Further, the molded article of this resin composition has excellent appearance and adhesion of the coating film.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 77/00-77/12 C08K 5/54 C08K 7/00-7/14

Claims (6)

(57) [Claims] 1. A thermoplastic polyamide resin (A) 60 to 9
Graft polymerization of one or more vinyl monomers to 9 parts by weight of a polyorganosiloxane rubber or to a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are entangled with each other so that they cannot be separated. Graft copolymers (B) 1-4
0 parts by weight, and 100 parts by weight of the total of both components (A) and (B), the silane compound (C) having an epoxy group in an amount of 0.1 part by weight.
A resin composition containing from 0.01 to 10 parts by weight. 2. The total of components (A), (B) and (C) is 1
The resin composition according to claim 1, further comprising 10 to 300 parts by weight of a filler based on 00 parts by weight. 3. The resin composition according to claim 1, wherein the number average particle diameter of the graft copolymer (B) is in the range of 0.08 to 0.6 μm. 4. The resin composition according to claim 1, wherein the vinyl monomer is a (meth) acrylate. 5. A silane compound having an epoxy group (C)
Is γ-glycidoxypropyltrimethoxysilane, γ-
Glycidoxypropylmethyldiethoxysilane and β-
The resin composition according to claim 1, which is at least one member selected from the group consisting of (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 6. The resin composition according to claim 2, wherein the filler is glass fiber or carbon fiber.