JP2002212400A - Thermoplastic resin composition and molded article using the same and used for automobile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition whose shrinkage factor has small anisotropy, when molded, and which has excellent impact resistance, moisture heat resistance, thermal expansion characteristics, rigidity and flowability, and to provide a molded article such as a large molded article, for example, an automotive outer plate. SOLUTION: This thermoplastic resin composition comprises (A) a thermoplastic polyester resin having an acid value of at least 1.5 mgKOH/g, (B) acrylonitrile/butadiene/styrene resin (ABC resin) (C) a composite rubber-based graft copolymer prepared by graft-polymerizing one or more vinylic monomers to a composite rubber comprising 10 to 90 wt.% of a polyorganosiloxane rubber component and 90 to 10 wt.% of a polyalkyl (meth)acrylate rubber component and having an average particle diameter of 0.08 to 0.6 μm, and (D-1) glass fibers and (D-2) glass flakes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an excellent impact resistance,
Thermoplastic resin composition having wet heat resistance, thermal expansion properties, rigidity, fluidity and low anisotropy of shrinkage during molding, resulting in improved warpage of molded articles, and automobiles using the same The present invention relates to a molded product for an outer plate.

[0002]

2. Description of the Related Art Polybutylene terephthalate (hereinafter referred to as P
Thermoplastic resin represented by BT) has excellent moldability, mechanical properties, heat resistance, electrical properties,
Since it has chemical resistance and the like, it is widely used in the fields of electric / electronics and automobiles.

However, the thermoplastic polyester resin has low impact resistance and a large molding shrinkage during injection molding. In particular, in the case of a thermoplastic polyester resin reinforced with glass fiber or the like, the flow of molten resin during molding is high. Since the shrinkage rate differs greatly between the direction and the direction perpendicular to the direction, the anisotropy is generated in the shrinkage rate, and warpage is likely to occur in the molded product. .
For this reason, it is a fact that it is not used particularly for automobile outer panels such as fenders, roofs, hoods and doors.

As a method of improving the anisotropy of the shrinkage at the time of molding, a method of adding a non-crystalline resin having a small shrinkage such as an ABS resin to reduce the shrinkage and reduce warpage (Japanese Patent Laid-Open No. 49-49) JP-A-97081, JP-A-50-23449, etc.) and a method using mica as a flat filler or glass beads as spherical particles (Japanese Patent Publication No. 49-49).
-18615, JP-A-57-16055,
JP-A-57-80447, JP-A-5-98138
And the like are disclosed.

[0005]

However, in these conventional methods, the effect of improving the anisotropy of the shrinkage during molding is small, the warpage is not sufficiently improved, and the impact resistance is reduced. In practice, the use of large molded products has been a major problem. An object of the present invention is to provide a resin composition having a small anisotropy of shrinkage during molding, and having excellent impact resistance, wet heat resistance, thermal expansion properties, rigidity and fluidity, and large molded articles such as automobile outer panels. To provide a molded article.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a thermoplastic polyester resin having an acid value in a specific range, an ABS resin,
By using a composite rubber of a polyorganosiloxane rubber graft-polymerized with a vinyl monomer and a polyalkyl (meth) acrylate rubber in combination with a specific inorganic filler, high impact resistance and excellent moisture and heat resistance are achieved. The present inventors have found that a resin composition having low anisotropy in shrinkage and having a small anisotropy can be obtained, which is suitable for large-sized molded articles.

That is, the present invention provides: At least a thermoplastic polyester resin (A) having an acid value of 1.5 mg KOH / g or less, and acrylonitrile /
Butadiene / styrene resin [ABS resin] (B), 10 to 90% by weight of a polyorganosiloxane rubber component and 90 to 10% of a polyalkyl (meth) acrylate rubber component
% By weight and having an average particle size of 0.08 to 0.6 μm
m, a composite rubber-based graft copolymer (C) obtained by graft-polymerizing one or more vinyl monomers onto the composite rubber, a glass fiber (D-1), and a glass flake (D). -2) a thermoplastic resin composition characterized by comprising:

[0008] 2. 100 parts of the thermoplastic resin composition
% By weight, the thermoplastic polyester resin (A) is 30 to 80% by weight, and the acrylonitrile / butadiene / styrene resin [ABS resin] (B) is 2 to 3%.
0% by weight, the composite rubber-based graft copolymer (C)
-20% by weight, the total amount of the glass fiber (D-1) and the glass flakes (D-2) is 10-50% by weight, and (D-1) / (D-2) = 10-60. / 90 ~
The thermoplastic resin composition according to the above 1, which is 40% by weight,

3. The thermoplastic polyester resin (A)
The intrinsic viscosity [η] measured at a temperature of 30 ± 0.1 ° C. using a mixed solvent of phenol / tetrachloroethane = 6/4 by weight is 0.6 to 1.0 dl / g. 3. The thermoplastic resin composition as described in 1 above, A molded product for an automobile outer panel, comprising the thermoplastic resin composition according to any one of the above 1 to 3,

[0010] 5. After setting a resin film covering one surface of a molded article in a mold, the thermoplastic resin composition according to any one of the above 1 to 3 is filled in the mold, and the resin film and the thermoplastic resin are mixed. The molded article according to the above 4, wherein the resin composition is integrated with the molded article,

6. The molded article according to the above 5, wherein the resin film has a multilayer structure including at least a colored resin layer,

7. After setting the resin film in which the print layer is formed in advance in the mold so that the back surface of the print layer is exposed in the mold, the thermoplastic resin composition according to any one of the above 1 to 3 is placed in the mold. Filling, the molded article according to the above 4, characterized in that the printed layer and the thermoplastic resin composition are integrated.

8. After applying a paint to the mold surface, the thermoplastic resin composition according to any one of the above 1 to 3 is filled in the mold, and the paint is transferred to the thermoplastic resin composition and integrated. The molded article according to 4 above,

9. A molded article made of the thermoplastic resin composition according to any one of the above 1 to 3 is pressed against a resin film on which a printed layer is formed in advance, and the printed layer and the molded article made of the thermoplastic resin composition are pressed. A molded article according to the above item 4, characterized by being integrated.

The thermoplastic polyester resin (A) in the present invention is not particularly limited. Examples thereof include at least one difunctional carboxylic acid component and at least one glycol component or oxycarboxylic acid component. And a thermoplastic polyester resin obtained by a polycondensation reaction with a polymer.

The bifunctional carboxylic acid component includes, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, adipic acid, or an ester formed by esterifying a carboxyl group thereof. And the like. Among them, an aromatic dicarboxylic acid or an ester-forming derivative obtained by esterifying the carboxyl group thereof is preferable, and in particular,
Terephthalic acid or terephthalic acid diester is preferred.

The glycol component is not particularly limited, but includes, for example, α, ω-alkylene glycol represented by the following general formula [1], among which ethylene glycol and 1,4-butane Diols are preferred.

[0018]

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Examples of the glycol component other than α, ω-alkylene glycol include neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, polyoxyethylene glycol, polyoxytetramethylene glycol, or a mixture thereof. And ester-forming derivatives obtained by esterifying the hydroxyl groups of the above.

In the present invention, it is preferable that 70 mol% or more of all the acid components or all the diol components constituting the thermoplastic polyester resin (A) is a single component.
The reason is that with such an amount, good chemical resistance and heat resistance can be obtained.

Among the thermoplastic polyester resins (A) composed of the above-mentioned components, a PBT resin is particularly preferred. PBT resin is usually
Manufactured from 1,4-butanediol and dimethyl terephthalate or terephthalic acid, and a third component such as a diol component such as 1,3-propanediol or ethylene glycol or a dicarboxylic acid other than terephthalic acid may be used at the time of manufacture. They may be co-condensed.

Such a thermoplastic polyester resin (A)
Is especially phenol / tetrachloroethane = 6/4
The intrinsic viscosity [η] measured at a temperature of 30 ± 0.1 ° C. using a mixed solvent in a weight ratio is preferably 0.6 to 1.0 dl / g. From 0.7 to 0.95 dl / g. Further, the acid value is preferably 1.5 mgKOH / g or less, and particularly preferably 1.0 mgKOH / g or less. If the acid value of the thermoplastic polyester resin (A) is more than 1.5 mgKOH / g, the wet heat resistance may decrease, which is not preferable.

The amount of the thermoplastic polyester resin (A) used is 30 parts based on the total amount of the thermoplastic resin composition of the present invention.
-80% by weight, preferably 40-70% by weight. If the amount of the thermoplastic polyester resin (A) is within such a range, the fluidity is good.

The ABS resin (B) in the present invention is a component (diene polymer) composed of a conjugated diene olefin rubber containing butadiene as a main component, and a vinyl cyanide monomer containing at least acrylonitrile and styrene as main components. A graft copolymer, a block copolymer, a random copolymer, or a mixture of these three components, which comprises a copolymer and an aromatic vinyl monomer.

The composition ratio of the diene polymer and the monomer in the ABS resin (B) is not limited, but the diene polymer is 10 to 40% by weight, the vinyl cyanide monomer and the aromatic vinyl The total amount of the monomers is preferably in the range of 90 to 60% by weight. When the amount of the diene polymer is within the above range, more excellent impact resistance and affinity can be obtained.

The composition ratio of the aromatic vinyl monomer and the vinyl cyanide monomer is not limited, but aromatic vinyl monomer / vinyl cyanide monomer = 50 to 90. / 50
10 to 10% by weight, particularly aromatic vinyl monomer / vinyl cyanide monomer = 60 to 80/40 to 20% by weight. The reason is that with such an amount, good chemical resistance and heat resistance can be obtained.

The amount of the ABS resin (B) used is 2 to 30% by weight, preferably 5 to 20% by weight, based on the total amount of the thermoplastic resin composition of the present invention. When the amount of the ABS resin (B) is within the above range, a more excellent warpage suppressing effect,
Can provide impact resistance, fluidity, and thermal stability.
Further, in the present invention, the thermoplastic polyester resin (A) and A
It is preferable that the weight ratio of the BS resin (B) is in the range of thermoplastic polyester resin (A) / ABS resin (B) = 50 to 90/50 to 10% by weight. When the weight ratio of the thermoplastic polyester resin (A) to the ABS resin (B) is within this range, excellent chemical resistance and good fluidity are obtained.

Next, the composite rubber-based graft copolymer (C) in the present invention comprises 10 to 90% by weight of a polyorganosiloxane rubber component and 90 to 10% by weight of a polyalkyl (meth) acrylate rubber component, and It is obtained by graft-polymerizing one or more vinyl monomers onto a composite rubber having an average particle diameter of 0.08 to 0.6 μm. In the present invention, polyalkyl (meth) acrylate rubber is a general term for polyalkyl acrylate rubber and polyalkyl methacrylate rubber.

Instead of the above composite rubber, a polyorganosiloxane rubber component and a polyalkyl (meth) acryl
Even if any one of the rubber components or a simple mixture thereof is used, the excellent characteristics of the thermoplastic resin composition of the present invention cannot be obtained, and the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber cannot be obtained. A resin composition having excellent impact resistance and molding fluidity can be obtained only by using it in the form of a composite rubber having a structure entangled with each other so that the components cannot be separated.

When the ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component in the composite rubber is within the above range, a resin composition having good surface appearance, impact resistance and fluidity can be obtained. Can be obtained.
That is, polyorganosiloxane rubber component / polyalkyl (meth) acrylate rubber component = 10-90 / 90
The range is preferably from 10 to 10% by weight, more preferably from 20 to 10% by weight.
80/80 to 20% by weight.

The average particle size of the composite rubber is 0.08 to
It is preferable that the average particle diameter is in the range of 0.6 μm, and if the average particle diameter is in such a range, more excellent impact resistance and appearance of the molded article can be obtained.

In order to produce a composite rubber having such an average particle diameter, an emulsion polymerization method is preferable. First, a latex of a polyorganosiloxane rubber is prepared, and then a monomer for synthesizing an alkyl (meth) acrylate rubber is prepared. A method of impregnating the polymer with rubber particles of a polyorganosiloxane rubber latex and then polymerizing the monomer for synthesizing the alkyl (meth) acrylate rubber.

The polyorganosiloxane rubber component constituting the above composite rubber can be prepared by emulsion polymerization using the following organosiloxane and a crosslinking agent, and in this case, a graft crosslinking agent can be used in combination. .

Examples of the organosiloxane include various organosiloxane cyclics having three or more membered rings, and among them, those having a three to six membered ring are preferable. Specifically, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
Dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane and the like can be mentioned, and these can be used alone or in combination of two or more. These are used in an amount of 50% by weight or more, preferably 70% by weight or more, in the polyorganosiloxane rubber component. If the amount of the organosiloxane used is less than this, the impact resistance may be reduced.

The cross-linking agent used for preparing the polyorganosiloxane rubber includes a cross-linking agent having three or more functionalities. For example, trialkoxyalkylsilane, trialkoxyarylsilane, and tetraalkoxysilane are used. Specific examples of such a crosslinking agent include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. As the crosslinking agent used in the present invention, tetraalkoxysilane is preferable, and tetraethoxysilane is particularly preferable.

As the graft-linking agent, compounds capable of forming units represented by the following general formulas [2] to [5] are used.

[0037]

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[0038]

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[0039]

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[0040]

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In the general formulas [2] to [5], 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 a number of 1 to 6.

(Meth) which can form a unit of the general formula [2]
Since acryloyloxysiloxane has a high grafting efficiency, it can form an effective graft chain, and is advantageous in terms of exhibiting impact resistance. Incidentally, methacryloyloxysiloxane is particularly preferred as an example capable of forming the unit of the general formula [2]. Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl Ethoxydiethylsilane,
γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane, and the like.

Examples of the unit capable of forming the unit of the general formula [3] include vinylsiloxanes.
Tetramethyltetravinylcyclotetrasiloxane is exemplified. As the unit capable of forming the unit of the general formula [4], p-vinylphenyldimethoxymethylsilane can be mentioned. Examples of the unit capable of forming the unit of the general formula [5] include γ-mercaptopropyldimethoxymethylsilane, γ
-Mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane and the like.

The amount of the graft crosslinking agent used is 10% by weight or less, preferably 0.5 to 5% by weight in the organosiloxane-based mixture, that is, the mixture for polymerization of polyorganosiloxane containing the organosiloxane and the crosslinking agent. %. If the amount of the graft crossing agent used is larger than this, the impact resistance may be reduced.

As the emulsifier, an anionic emulsifier is preferable, and sodium alkylbenzene sulfonate, sodium lauryl sulfonate, sodium sulfosuccinate,
An emulsifier selected from sodium polyoxyethylene nonyl phenyl ether sulfate is used. Particularly, sulfonic acid emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable.

These emulsifiers are usually used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the organosiloxane mixture.
Used in parts by weight. By using these emulsifiers in this range, it is possible to maintain a stable dispersion state with a fine particle diameter and to eliminate coloring caused by the emulsifier.

The polyorganosiloxane latex thus produced is impregnated with a monomer for synthesizing a polyalkyl (meth) acrylate rubber, that is, an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate. By polymerizing these, a composite rubber can be obtained.

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n
-Propyl acrylate, n-butyl acrylate, 2
Alkyl acrylates such as ethylhexyl acrylate
And alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate and n-lauryl methacrylate, with n-butyl acrylate being particularly preferred.

Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4- Butylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Among the monomers for synthesizing the polyalkyl (meth) acrylate rubber, the polyfunctional alkyl (meth) acrylate is preferably 0.1 to 20% by weight, particularly preferably 0.5 to 10% by weight, and the remainder is It is an alkyl (meth) acrylate. When the amount of the polyfunctional alkyl (meth) acrylate used is in this range, more excellent impact resistance can be obtained.

The alkyl (meth) acrylate and the polyfunctional alkyl (meth) acrylate are used alone or in combination of two or more.

In the practice of the present invention, the polyorganosiloxane rubber component obtained by using octamethyltetracyclosiloxane as the dialkylorganosilane and γ-methacryloyloxypropyldimethoxymethylsilane as the siloxane grafting agent is used. It is preferable to use a composite rubber in which a polyalkyl (meth) acrylate rubber component whose main skeleton has a repeating unit of n-butyl acrylate is composited.

The composite rubber thus produced by the emulsion polymerization method can be graft-copolymerized with a vinyl monomer. Examples of the vinyl monomer to be graft-polymerized on the composite rubber include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene; methacrylic acids such as methyl methacrylate and 2-ethylhexyl methacrylate; Esters: Various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and these can be used alone or in combination of two or more. The graft component may be used in the form of a copolymer composed of two or more types.

The composite rubber-based graft copolymer (C) can be obtained by adding a vinyl-based monomer to the composite rubber latex and polymerizing it in one or more stages by a radical polymerization technique. The ratio of the composite rubber and the vinyl monomer when obtaining the composite rubber-based graft copolymer (C) is as follows:
The composite rubber is 10 to 95% by weight, preferably 20 to 90% by weight, and the vinyl monomer is 90 to 5% by weight, preferably 80 to 10% by weight based on the weight of the obtained graft copolymer. % By weight. If the vinyl monomer is in such a range, more excellent impact strength can be provided.

Glass fiber (D-1) used in the present invention
Is glass fiber made of non-alkali glass, and preferably has a weight average aspect ratio of 10 or more. Further, in order to improve the adhesion between the thermoplastic polyester resin (A) and the glass fiber (D-1), the glass fiber treated with a coupling agent such as a silane coupling agent or a titanate coupling agent. Is preferred. Further, the diameter of the glass fiber (D-1) is preferably φ15 μm or less, and particularly preferably φ13 μm or less.

The glass flake (D-2) used in the present invention has a weight average flake diameter before mixing of 40 to 40.
1400 μm, weight average aspect ratio of 10 to 100
Is a very thin plate-like reinforcing material, and usually uses alkali-free glass flakes. Further, it is preferable to use the above-mentioned coupling agent in order to improve the adhesion between the thermoplastic polyester resin (A) and the glass flake (D-2). The glass flake (D-2) preferably has an aspect ratio of 20 or more and a weight average particle size of 50 μm or more.

In the present invention, the glass fiber (D-1) and the glass flake (D-2) are always used in combination. The mixing ratio of glass fiber (D-1) and glass flake (D-2) is glass fiber (D-1) / glass flake (D-2).
= 10-60 / 90-40% by weight, preferably (D-1) / (D-2) = 20-50 / 80-50% by weight. Glass fiber (D-1) and glass flake (D
If the compounding ratio of -2) is in such a range, more excellent characteristics such as fluidity, toughness, warpage of a molded product, and mechanical strength can be obtained.

Further, in the thermoplastic resin composition of the present invention, glass fiber (D-1) and glass flake (D-2)
Is preferably 10 to 50% by weight, more preferably 20 to 45% by weight. If the amount is within such a range, good fluidity and excellent mechanical strength can be obtained.

Further, the thermoplastic resin composition of the present invention includes:
Thermoplastic resins and thermosetting resins other than the thermoplastic polyester resin (A) and the ABS resin (B) may be used at 30% by weight or less. Various thermoplastic resins and thermosetting resins used at this time include polyamide, polyurethane, polyethylene, polypropylene, polystyrene, AS, PVC, POM, and polycarbonate.
Bone, polysulfone, polyethersulfone, polyphenylene sulfide, polyphenylene oxide,
Polyethylene naphthalate, polybutylene naphthalate
, PCT, thermoplastic resin such as liquid crystal polymer; vinyl ester resin, unsaturated polyester resin, melamine resin,
Thermosetting resins such as benzoguanamine resin, diallyl phthalate resin, alkyd resin, phenol resin, epoxy resin, polyimide resin; SBR, hydrogenated SBR, NB
It is also possible to add an impact modifier such as R, hydrogenated NBR, ethylene-propylene copolymer, silicone rubber, fluorine-based rubber, polyester-based elastomer, polyamide-based elastomer and the like.

Further, a stabilizer, a plasticizer, a lubricant, a flame retardant, a pigment and the like can be added to the thermoplastic resin composition of the present invention, if necessary. Specifically, hindered phenol-based, phosphite-based, thioether-based heat stabilizers; lubricants such as ester wax, polyethylene wax, and polypropylene wax, and release agents; triphenyl phosphate, tricresyl Phosphate flame retardants such as phosphate; bromine flame retardants such as decabromobiphenyl and decabromophenyl ether; flame retardant aids such as antimony trioxide; pigments such as titanium oxide, zinc sulfide and zinc oxide; asbestos other than the present invention , Wollastonite, talc, and other fillers; and metal powders such as aluminum powder.

The thermoplastic resin composition of the present invention can be obtained by a known method and comprises the above (A), (B), (C),
A method of dry-blending each component (D-1) and (D-2) and other components using, for example, a blender or a mixer, a method of melt-mixing using an extruder, and the like are mentioned. And a method of melt-mixing using a screw extruder, extruding into a strand, and pelletizing.

The thermoplastic resin composition of the present invention can be easily molded by various molding methods such as injection molding, extrusion molding, compression molding and the like, and has excellent fluidity, so that it is particularly suitable for injection molding. Further, since it has excellent mechanical properties, it is particularly useful for molded articles for automobile outer panels and can be used for molded articles for other uses.

As described above, various pigments can be added to the resin composition of the present invention, whereby it is possible to obtain a molded article having a good design. Also, because it has excellent fluidity, after setting any resin film in the mold,
It is also suitable for so-called film insert molding in which a resin is filled in a mold and integrated with a film, and a molded product having no surface defect and excellent surface quality can be obtained. The resin film may be a transparent film made of a transparent resin or a multi-layered colored film including a colored layer. When a colored film is used, a molded article excellent in design can be obtained without concern for the color of the resin. Usually, when obtaining a large molded product by such insert molding, in order to fill the resin in every corner of the mold, the mold is often provided with a multi-point gate,
Welding frequency increases, and appearance defects such as wrinkles are likely to occur. The resin composition of the present invention has a great advantage that a molded article having excellent surface quality can be obtained without using a complicated mold design without using a multipoint gate because of its good fluidity.

As a method for obtaining a molded article having excellent design properties using the resin composition of the present invention, in addition to the above-described method, a resin film having a printed layer formed in advance may be placed in a mold with a printed layer. After setting so that the back side of the mold is exposed in the mold, filling the mold with resin and integrating it with the print layer, obtaining a molded product with the printed layer transferred, or applying a paint on the mold inner surface in advance, and then mold There is a method of obtaining a molded article having a coating film on the surface by filling the inside with a resin and integrating with a paint. In these cases, similarly to the above, a molded article excellent in surface quality and design can be obtained without requiring complicated mold design because of the good fluidity of the thermoplastic resin composition of the present invention. Alternatively, it is also possible to use a hydraulic transfer method or the like in which a molded article is formed in advance, pressed against a resin film on which a print layer is formed in advance, and the print layer and the molded article are integrated.

[0064]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist thereof. In the following, all parts and percentages are by weight unless otherwise specified. In addition, the x mark described in the measured value of the comparative example means that it is significantly inferior.

[Method of Measuring Acid Value of Thermoplastic Polyester Resin] 1.0 to 2.0 g of a thermoplastic polyester resin was precisely weighed into a 200 ml Erlenmeyer flask, 60 ml of benzyl alcohol was added, and the inside of the Erlenmeyer flask was flushed with nitrogen gas. Immediately after the replacement, the flask is sealed with aluminum foil, and the resin is dissolved while immersing the Erlenmeyer flask in a constant temperature oil bath at 160 ° C. and vibrating. After confirming complete dissolution, a 0.1% bromothymol / ethanol solution was added, a stirrer was placed in an Erlenmeyer flask, and the mixture was heated and stirred on a heating stirrer while stirring 1 / 50N potassium hydroxide / ethanol. Titrate with benzyl alcohol solution. The end point of the titration was the time when yellow changed to yellow-green. The acid value is calculated according to the following equation.

Acid value (mgKOH / g) = [(V−V0) × F × 1.122] / SV (ml): titration of 1 / 50N potassium hydroxide / benzyl alcohol solution in sample V0 (ml): titration of blank 1 / 50N potassium hydroxide / benzyl alcohol solution F: factor of 1 / 50N potassium hydroxide / benzyl alcohol solution S (g): weight of sample

[Measurement method of flexural strength] The flexural strength and flexural modulus were measured by an injection molding machine to have a length of 127 mm and a width of 1 mm.
A rod-shaped test piece having a thickness of 2.7 mm and a thickness of 3.01 mm was formed.
According to ASTM D-790, the load speed is 5 mm / min,
Shimadzu Autograph AG500 with 50mm distance between spans
It measured using 0.

[Measurement Method of Izod Impact Value] Using an injection molding machine, length 127 mm, width 12.7 mm, thickness 3.
A bar-shaped test piece of 01 mm was formed, and this test piece was cut in half in the longitudinal direction, and a V-notch was formed on the gate side by cutting to obtain a notched test piece. The measurement temperature was 23 ℃ and -20 ℃.
At this point, Izod impact values were measured according to ASTM D-256.

[Method of Measuring Spiral Flow Length] A spiral mold having a sectional shape of 6.4 mm in width and 1.6 mm in thickness was used to measure the spiral flow length under the following conditions. Molding machine Toshiba IS50AM Cylinder temperature 260 ° C Mold temperature 60 ° C Pressure 60kg / cm ² Injection speed C-0 Cooling time 15 seconds Injection time 5 seconds Weighing 45mm

[Method for Evaluating Moisture / Heat Resistance] A bending test piece was 12
After standing at 1 ° C. and under a saturated steam pressure of 1.1 kg / cm ² for 48 hours, the flexural strength was measured, and the flexural strength before and after leaving was measured, and the flexural strength retention was evaluated.

[Method of Evaluating Shrinkage Anisotropy] A cylinder having a temperature of 250 ° C., a mold of 60 ° C., and a length of 10
Using a mold having a film gate of 5 mm × width 50 mm × thickness 2.0 mm and thickness 1 mm, a molded sheet having the above shape is formed, and the dimension in the direction perpendicular to the flow direction is measured with a caliper.
The shrinkage was determined. The anisotropy of the shrinkage was evaluated based on the ratio of the shrinkage in the flow direction / perpendicular direction (the closer to 1, the smaller the anisotropy).

[Measurement Method of Linear Thermal Expansion Coefficient] The test piece for bending test described above was cut into a length of 5 mm and a width of 5 mm.
The coefficient of linear expansion in the flow direction at 30 ° C to 100 ° C was measured using TMA4000S manufactured by Mac Science.

<< Examples 1-6 >> and << Comparative Examples 1-6 >>
Intrinsic viscosity 0.7 dl / g, acid value: 1.1 mgKOH / g
PBT resin (A-1) and ABS resin (B) as acrylonitrile / butadiene / styrene = 30/20 /
50% by weight of an ABS resin and 60% by weight of a polyorganosiloxane rubber and 24% by weight of a polyalkyl (meth) acrylate rubber as a composite rubber-based graft copolymer (C) having an average particle size of 0.16 μm. Graft copolymer components (acrylonitrile 30% by weight, styrene 7
(Acrylonitrile / styrene copolymer consisting of 0% by weight) = composite rubber graft copolymer consisting of 16% by weight, glass fiber (D-1) having a diameter of 13 μm, glass fiber (D-2) A glass flake having a weight-average particle size of 140 μm was blended in the ratio shown in Table 1 and stirred with a tumbler for 10 minutes. This compound was kneaded at 250 ° C. using a 40 mm vent type single screw extruder (manufactured by IKG Co., Ltd.), extruded into strands, pelletized, and the pellets were subjected to the test described above using an injection molding machine. Each piece was molded and evaluated according to the measurement method. As a comparative example, the same raw materials as in Example 1 were used, blended at the ratio shown in Table 2, and molded into a test piece.
Was evaluated in the same way as Table 1 shows the results of Examples 1 to 6, and Table 2 shows the results of Comparative Examples 1 to 6. It turns out that the composition of the present invention has excellent fluidity, toughness and mechanical strength.

[0074]

[Table 1]

[0075]

[Table 2]

<< Examples 7 to 8 >> and << Comparative Example 7 >> Instead of the PBT resin (A-1) used in Example 1, Table 3 was used.
Table 4 using PBT resins (A-2) to (A-4) shown in
, And Examples 7 to 8 and Comparative Example 7 were performed and evaluated in the same manner as in Example 1. Table 4 shows the results. It is understood that the composition of the present invention is a material having a good balance in fluidity and toughness, and is excellent in wet heat resistance.

[0077]

[Table 3]

[0078]

[Table 4]

Example 9 and Comparative Examples 8 to 9 Parts having a rear fender shape were molded and evaluated.
The parts are molded by setting a commercially available resin colored film (made by Mitsubishi Chemical MKV Co., Ltd .: dry paint film AVLOY, thickness of about 0.6 mm, backing ABS), which has been previously shaped by a vacuum forming machine, in a mold. The resin was filled in the mold with an injection molding machine having a clamping force of 5000 tons. Using the same composition as Example 3 and Comparative Example 4 as the resin material,
Example 9 and Comparative Example 8 were used. In addition, a commercially available PC / ABS material (Mitsubishi Engineering Link Plastic Co., Ltd.):
Comparative Example 9 was molded in the same manner using PM1210). The obtained rear fender-shaped part has an average thickness of about 3.
5 mm. A test piece was cut out from a substantially smooth surface of the part having a thickness of about 5 mm, and the following evaluation was performed. Table 5 shows the evaluation results.

[Evaluation Method of Deformation / Warpage] The difference between the actual part shape and the design shape was visually confirmed.

[Method of Evaluating Surface Quality] The presence or absence of appearance defects such as wrinkles and cracks on the component surface was visually confirmed.

[Measurement method of flexural modulus] The width of the test piece was 1
0 mm, load speed 2 mm / min, span distance 48.
The flexural modulus was measured using a Mitsubishi Kasei fully automatic bending tester at 5 mm and a measurement temperature of 23 ° C. in accordance with ISO R-178.

[Method of Measuring Izod Impact Value] The width of the test piece was 10 mm, and a V-notch was formed by cutting to obtain a notched test piece. The measurement temperature was -30 ° C, and ISO R-18
0, variable temperature impact tester No. 195-
Izod impact values were measured using LFR.

[Method of Measuring Average Linear Expansion Coefficient] A test piece was processed into a prism having a length of 15 mm and a side length of about 5 mm.
The average linear coefficient of expansion at −30 ° C. to 130 ° C. is determined according to JIS K7
According to 197, it was measured using a Seiko TMA instrument.

[0085]

[Table 5]

When the composition of the present invention is used, a large molded product having small deformation / warpage, excellent surface quality, and excellent rigidity, impact resistance and thermal expansion characteristics can be obtained.

[0087]

According to the present invention, it is possible to provide a composition having excellent toughness, especially low-temperature impact value, low anisotropy of shrinkage, and excellent fluidity, wet heat resistance, thermal expansion properties and rigidity. . Therefore, since the composition of the present invention is suitable for large-sized molded articles, it is particularly useful for automobile outer panels.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/00 CFD C08J 5/00 CFD C08K 7/00 C08K 7/00 7/14 7/14 C08L 51 / 08 C08L 51/08 55/02 55/02 (72) Inventor Masao Nakajima 2 Takara-cho, Kanagawa-ku, Yokohama, Kanagawa Prefecture Inside Nissan Motor Co., Ltd. (72) Inventor Koichi Handa 2 Takara-cho, Kanagawa-ku, Yokohama, Kanagawa 2 F-term in stock (reference) 4F071 AA12 AA12X AA22 AA22X AA33 AA33X AA34 AA34X AA44 AA45 AA46 AA67 AA77 AB28 AD01 AD05 AH07 BB03 BB05 BB06 BC07 4F100 AG00A AK01B AK41A02A03A02A01A04B HB31B JA20A JD04 JJ03 JK01 JK10 JL04 JL10B YY00A 4J002 BN123 BN152 BN173 CF031 CF041 CF051 CF061 CF071 CF081 CF181 CP173 DL006 DL007 FA017 FA046 FD010 FD060 FD090 FD130 FD160 FD170 GN00

Claims (9)

[Claims] An acid value of at least 1.5 mg KOH /
g of thermoplastic polyester resin (A) and acrylonitrile / butadiene / styrene resin [ABS resin]
(B) and a polyorganosiloxane rubber component 10 to 90
% By weight and a polyalkyl (meth) acrylate rubber component of 90 to 10% by weight and having an average particle size of 0.0
A composite rubber-based graft copolymer (C) obtained by graft-polymerizing one or more vinyl monomers to a composite rubber having a thickness of 8 to 0.6 μm, a glass fiber (D-1), -A thermoplastic resin composition characterized by comprising (D-2). 2. The thermoplastic polyester resin (A) when the whole of the thermoplastic resin composition is 100% by weight.
Is 30 to 80% by weight, the acrylonitrile / butadiene / styrene resin [ABS resin] (B) is 2 to 30% by weight, and the composite rubber-based graft copolymer (C) is 2 to 20% by weight.
% By weight, the glass fiber (D-1) and the glass fiber
The total amount of the solid (D-2) is 10 to 50% by weight, and (D-1) / (D-2) = 10 to 60/90 to 40% by weight. The thermoplastic resin composition according to the above. 3. The thermoplastic polyester resin (A)
The intrinsic viscosity [η] measured at a temperature of 30 ± 0.1 ° C. using a mixed solvent of phenol / tetrachloroethane = 6/4 by weight is 0.6 to 1.0 dl / g. The thermoplastic resin composition according to claim 1, wherein: 4. A molded article for an automobile outer panel, comprising the thermoplastic resin composition according to claim 1. 5. A resin film covering one surface of a molded article is set in a mold, and then the thermoplastic resin composition is filled in the mold, and the resin film and the thermoplastic resin composition are mixed. The molded article according to claim 4, wherein the molded article is integrated. 6. The resin film according to claim 5, wherein the resin film has a multilayer structure including at least a colored resin layer.
The molded article as described. 7. A resin film on which a print layer is formed in advance is set in a mold so that the back surface of the print layer is exposed in the mold, and then the thermoplastic resin composition is filled in the mold, and the printing is performed. The molded article according to claim 4, wherein the layer and the thermoplastic resin composition are integrated. 8. The method according to claim 1, wherein after the coating is applied to the inner surface of the mold, the thermoplastic resin composition is filled in the mold, and the coating is transferred to and integrated with the thermoplastic resin composition. 4. The molded article according to 4. 9. A molded article made of the thermoplastic resin composition is pressed against a resin film on which a print layer is formed in advance,
The molded product according to claim 4, wherein the printed layer and the molded article made of the thermoplastic resin composition are integrated.