JP3339086B2 - Thermoplastic resin composition and resin molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition using an olefin resin or the like and a resin molded article obtained by molding the same into a predetermined shape and useful as an automobile part such as a bumper.

[0002]

2. Description of the Related Art Thermoplastic resins such as engineering plastics, vinyl polymers and olefin polymers are widely used as various molded products because of their excellent physical properties and moldability. However, thermoplastic resins generally have problems with paintability, coating film adhesion, weather resistance, and the like, and improvements are required.

For example, a propylene polymer has excellent properties such as mechanical properties, moldability and processability, and chemical resistance, and is inexpensive. There is a problem. Therefore, for example, when used in a bumper of an automobile, a thermoplastic elastomer for improving impact resistance and coating properties is added to a propylene-based polymer (JP-A-63-39951, JP-A-63-39551). 63-1
22752). And as the painting method,
2. Description of the Related Art A method of cleaning the surface of a molded article using a halogen-containing organic solvent such as 1,1,1, -trichloroethane, trichloroethylene or the like, followed by primer coating and overcoating is widely used.

Further, in order to improve the above-mentioned disadvantages of the propylene polymer, a vinyl polymer,
For example, polystyrene is blended. JP-A-58-93730 discloses an attempt to disperse polystyrene in a propylene-based polymer by blending a polystyrene-modified propylene-based polymer produced by a specific method with a propylene-based polymer. Further, Japanese Patent Application Laid-Open Nos. 2-173049 and 4-77953 describe a composition in which a multi-phase structure comprising an olefin-based copolymer and a vinyl-based copolymer is blended with a propylene-based polymer. Is disclosed.

[0005]

However, at present,
In terms of environmental problems, it is desired to omit the surface cleaning step using a halogen-containing organic solvent. However, if the surface cleaning is not performed, there is a problem that the adhesion to the primer is extremely reduced. Was.

[0006] Because propylene-based polymers and polystyrene generally have poor compatibility, polystyrene can only be blended in small amounts with propylene-based polymers. Therefore, there was a problem that the impact resistance of the molded product of this blend tends to decrease.

In the composition disclosed in JP-A-58-93730, the grafting efficiency of a polystyrene-modified propylene-based polymer is also low, so that the compatibility when blended with the propylene-based polymer is insufficient. There was a problem.

Further, in the compositions disclosed in JP-A-2-173049 and JP-A-4-77953,
The method of adding a multi-phase structure graft copolymer consisting of an olefin-based copolymer and a vinyl-based copolymer improves the compatibility with the propylene-based polymer, but has a poor affinity with the paint, so that the paint is applied. However, there has been a problem that the properties, that is, the ease of coating when applying the coating material to the base material are still insufficient.

The present invention has been made in view of the above-mentioned conventional problems, and an object thereof is to provide a good coating film while maintaining the characteristics of a thermoplastic resin such as good mechanical properties and moldability. An object of the present invention is to provide a thermoplastic resin composition and a resin molded product having adhesion, impact resistance, weather resistance, and improved coating properties.

[0010]

In order to achieve the above object, the first invention provides (1) at least one or more thermoplastic resins selected from the group consisting of nonpolar α-olefin resins and crystalline resins. And (2) a copolymer (A segment) formed from a nonpolar α-olefin monomer and a polar vinyl monomer, and a vinyl polymer formed from at least one vinyl monomer. A multi-phase structure graft copolymer, which comprises a copolymer or a copolymer (B segment), wherein one segment forms a dispersed phase as fine particles in the other segment, and the component (1) The gist of the present invention is a thermoplastic resin composition having a melt viscosity ratio of 0.05 or more of the component and the component (2).

In the second invention, a gist of the invention is a thermoplastic resin composition obtained by blending a thermoplastic elastomer with the thermoplastic resin composition of the first invention. In the third invention, a gist of the invention is a resin molded product obtained by molding the thermoplastic resin composition of the first invention or the second invention into a predetermined shape.

Next, each component of the present invention will be described in detail. The component (1) used in the present invention, that is, at least one or more thermoplastic resins selected from the group consisting of non-polar α-olefin resins and crystalline resins, is excellent in mechanical properties, but has good paintability and coating film adhesion. Because it is inferior,
Modification is required. Among them, non-polar α-
The olefin resin is a homopolymer of a non-polar α-olefin monomer or a copolymer of two or more monomers. Specifically, homopolymers such as ultra-low density, low density, medium density, high density polyethylene, propylene polymer, polybutene-1, poly-4-methylpentene, ethylene copolymer, and propylene copolymer In particular, there is a particularly high demand for improvement of a propylene-based polymer, which is preferable. In addition, these thermoplastic resins (1) may be mixed and used.

The propylene-based polymer is a crystalline polypropylene, and refers to a propylene homopolymer and a copolymer mainly composed of propylene and another α-olefin. In these homopolymers or copolymers, it is desirable to contain propylene at 75% by weight or more.

Specifically, for example, isotactic polypropylene, crystalline propylene-ethylene random copolymer, crystalline propylene-ethylene block copolymer,
A typical example is a crystalline propylene-butene-1 random copolymer. These propylene-based polymers can be used as a mixture. Further, other polymers can be mixed and used as long as the properties of the propylene-based polymer are not impaired.

The crystalline resin constituting the thermoplastic resin (1) includes, for example, polyamide resin, polyester resin, polyoxymethylene resin, polyphenylene sulfide resin and the like.

The polyamide resin used in the present invention includes nylon 6, nylon 6.6, nylon 6.10, nylon 6.12, nylon 11, nylon 12, nylon 4.
・ Aromatic polyamide resins such as aliphatic polyamide resins such as 6, polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, xylene group-containing polyamides, and their modified products or mixtures thereof. . Particularly preferred polyamide resins are nylon 6, nylon 6.6 and the like.

Specific examples of the polyester resin used in the present invention include polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate. More preferred are polyethylene terephthalate and polybutylene terephthalate.

The polyoxymethylene resin used in the present invention includes substantially only oxymethylene units produced from a cyclic oligomer such as a formaldehyde monomer or its trimer (trioxane) or tetramer (tetraoxane). Oxymethylene homopolymer consisting of the above raw materials and cyclic ethers such as ethylene oxide, propylene oxide, epichlorohydrin, 1,3-dioxolane, glycol homomers and diglycol homomers.
Oxymethylene unit and carbon number 2
Oxymethylene copolymers comprising the above oxyalkylene units are included.

The polyphenylene sulfide resin used in the present invention is a resin represented by the following formula 1.

[0020]

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The production method is, as disclosed in JP-B-54-3368, a method of reacting paradichlorobenzene and sodium sulfide in an N-methylpyrrolidone solution at 160 to 250 ° C. under a predetermined pressurizing condition. Adopted.

Next, the component (2) referred to in the present invention, that is, the multiphase graft copolymer is a copolymer obtained from a non-polar α-olefin monomer and a polar vinyl monomer, usually In a matrix of an olefin-based copolymer (A segment) or a vinyl-based polymer or a copolymer (hereinafter, a polymer or a copolymer is referred to as a (co) polymer) (B segment), the B segment or the A segment is spherical. But not limited thereto.

The polymer obtained from the non-polar α-olefin monomer can easily adjust the fluidity by changing the molecular weight and the like, so that the vicinity of the surface of the molded article obtained by molding the thermoplastic resin composition is obtained. Oriented. In addition, since the polymer has excellent compatibility with the component (1), there is no possibility that the mechanical properties are impaired. On the other hand, it is necessary to introduce a polar component in order to improve coating film adhesion and coating properties,
In a polymer obtained from only a polar vinyl-based monomer, the polar component is not efficiently oriented near the surface. Therefore, the non-polar α
-A copolymer obtained by copolymerizing an olefin monomer and a polar vinyl monomer can effectively exhibit both properties.

The dispersed polymer particles are fine and the particle size is preferably 0.001 to 10 μm.
m, more preferably 0.01 to 5 μm. When the dispersed resin particle diameter is less than 0.001 μm or 10 μm
When it exceeds, the dispersibility when blended with the thermoplastic resin (1) is poor, for example, the appearance is deteriorated, the impact resistance is reduced,
Or, it is not preferable because the effect of improving the paintability and the like is insufficient. The term "paintability" as used herein refers to the ease of painting when a paint is applied to a substrate, and when paintability is good, "repelling" does not occur during painting, so that the appearance is good. Conversely, if the paintability is poor, the paint will "repel", resulting in flow marks and poor appearance. Normal,
If the polarity of the substrate is low, the coatability tends to be poor.

The number average degree of polymerization of the vinyl polymer in the multiphase graft copolymer (2) in the present invention is usually 5
5,000, preferably 10-1,000. More preferably, it is in the range of 10 to 600. When the number average polymerization degree is less than 5, the thermoplastic resin composition (1)
Is not preferred because of poor compatibility with On the other hand, if the number average degree of polymerization exceeds 5,000, the melt viscosity is high, and the moldability and the surface gloss are undesirably reduced.

The non-polar α-olefin monomer in the copolymer obtained from the non-polar α-olefin monomer and the polar vinyl monomer in the multiphase structure graft copolymer (2) is ethylene. Propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1 and the like. The polar vinyl monomer is a non-polar α-
A polar monomer having a vinyl group copolymerizable with an olefin monomer.

Examples of the polar vinyl monomer include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride,
Itaconic acid, itaconic anhydride, bicyclo (2,2,1)
Α, β-unsaturated carboxylic acids such as -5-heptene 2,3-dicarboxylic acid and metal salts thereof, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, acrylic 2-ethylhexyl acid, methyl methacrylate, ethyl methacrylate,
Α, β-unsaturated carboxylic esters such as n-butyl methacrylate and isobutyl methacrylate, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc. Examples thereof include unsaturated glycidyl group-containing monomers such as vinyl esters, glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.

The ratio of the non-polar α-olefin monomer to the polar vinyl monomer in the copolymer obtained from the non-polar α-olefin monomer and the polar vinyl monomer is not particularly limited. The amount of the monomer is preferably 1% by weight or more and 80% by weight or less.

Specific examples of the copolymer comprising a non-polar α-olefin monomer and a polar vinyl monomer include ethylene-
Acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate Polymer, ethylene-ethyl 2-ethylhexyl acrylate copolymer, ethylene-methyl ethyl methacrylate, ethylene-isopropyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer, Ethylene-methacrylic acid 2
-Ethylhexyl copolymer, ethylene-vinyl acetate copolymer or saponified product thereof, ethylene-vinyl propionate copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene-ethyl acrylate-glycidyl methacrylate Copolymers, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer and the like can be mentioned. These copolymers can be used as a mixture.

In the present invention, the vinyl monomer constituting the vinyl copolymer in the multiphase graft copolymer is a vinyl aromatic monomer such as styrene, a nucleus-substituted styrene such as methylstyrene, dimethylstyrene. , Ethyl styrene, isopropyl styrene, chlorostyrene,
α-substituted styrene such as α-methylstyrene, α-ethylstyrene, (meth) acrylate monomer such as (meth) acrylic acid such as methyl (meth) acrylate and ethyl (meth) acrylate, and 1 carbon atom To 20 alkyl esters, (meth) acrylonitrile, and vinyl ester monomers such as vinyl acetate and vinyl propionate.

Further, maleimides such as vinyl halide or vinylidene halide (particularly, vinyl chloride or vinylidene chloride), vinyl naphthalene, vinyl carbazole, phenyl or cyclohexyl, and other vinyl monomers can be used. In the multiphase graft copolymer (2) of the present invention, the A segment is preferably 5 to 99% by weight,
More preferably from 20 to 95% by weight,
The segments preferably comprise from 95 to 1% by weight, more preferably from 80 to 5% by weight.

When the content of the A segment is less than 5% by weight, the amount of orientation of the graft copolymer on the surface of the molded product decreases,
Paintability and coating film adhesion tend to be insufficient. If the A segment exceeds 99% by weight, the compatibility with the thermoplastic resin (1) tends to be insufficient, which is not preferable.

The grafting method for producing the multi-phase structure graft copolymer (2) may be any of generally known methods such as a chain transfer method and an ionizing radiation irradiation method. , According to the following method. Because the grafting efficiency is high and secondary aggregation due to heat does not occur, the expression of performance is more effective,
Also, this is because the manufacturing method is simple.

Next, the method for producing the thermoplastic resin composition of the present invention will be specifically described. That is, 100 parts by weight of copolymer particles obtained by synthesizing a non-polar α-olefin monomer and a polar vinyl monomer are suspended in water to prepare an aqueous suspension. Separately, 1 to 400 parts by weight of at least one vinyl monomer is mixed with one or a mixture of two or more radically polymerizable organic peroxides represented by the following chemical formulas 2 or 3. Radical polymerization of a polymerization initiator having a decomposition temperature of 40 to 90 ° C. for obtaining a half-life of 10 hours with respect to 0.1 to 20 parts by weight based on 100 parts by weight of a vinyl monomer and a vinyl monomer. A solution prepared by dissolving 0.01 to 5 parts by weight with respect to a total of 100 parts by weight of the neutral organic peroxide. This is then added to the aqueous suspension.

Next, the copolymer particles are heated under a condition that the decomposition of the polymerization initiator does not substantially occur, so that the vinyl monomer, the radically polymerizable organic peroxide and the polymerization initiator are impregnated in the copolymer particles. When the impregnation rate reaches the initial 50% by weight or more, the temperature of the aqueous suspension is increased, and the vinyl monomer and the radical polymerizable organic peroxide are mixed in the copolymer particles. It is polymerized or copolymerized to obtain a grafted precursor. This grafting precursor is used in an amount of 100 to 300.
By melt-kneading at a temperature of ° C., a multiphase structure graft copolymer (2) composed of an A segment and a B segment is obtained.

The grafting precursor does not necessarily have to be melt-kneaded before being mixed with the thermoplastic resin (1). That is, the grafting precursor may be directly melt-mixed with the thermoplastic resin (1). This is because the grafting precursor becomes a graft copolymer by melt-kneading.

Further, the same copolymer as the A segment and the same (co) polymer as the B segment are separately mixed with the grafting precursor, or one of the (co) polymers is mixed and melted. To obtain a multiphase graft copolymer (2). Furthermore, in the above polymerization process, a grafting precursor is synthesized without using a vinyl monomer, and the grafting precursor and the vinyl monomer are mixed and melt-kneaded. (2) can be obtained. Most preferred is the multi-phase structure graft copolymer (2) obtained by melt-kneading the grafting precursor.

The thermoplastic resin composition of the present invention can be obtained by melt-kneading the thus obtained multi-phase structure graft copolymer (2) and the thermoplastic resin (1).
Here, the melt viscosity ratio of component (1) to component (2) (ratio of component (1) / component (2)) must be 0.05 or more when measured under the same conditions. This ratio is 0.0
When it is less than 5, the multiphase structure graft copolymer hardly exists near the surface of the resin molded product, and the coating film adhesion and coating property become insufficient. The melt viscosity ratio of this component (1) / component (2) is preferably at least 0.5, most preferably at least 1.

Here, the melt viscosity refers to the viscosity when a thermoplastic resin is melted at the same temperature and extruded under a load. The melt viscosity ratio refers to the ratio of the melt viscosities of the component (1) and the component (2) under the same load. The degree of orientation of the multi-phase structure graft copolymer in the vicinity of the surface of the molded article is determined by an analysis method using an X-ray photoelectron spectrometer (ESCA) or an analysis method using an infrared absorption spectrum (IR
Method) and other analytical methods.

The radical polymerizable organic peroxide is a compound represented by the following general formula 2.

[0041]

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In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R
₄ represents an alkyl group having 1 to 4 carbon atoms, and R ₅ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms.
m is 1 or 2.

The radically polymerizable organic peroxide is a compound represented by the following general formula (3).

[0044]

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In the formula, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and R
₉ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₀ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms.
n is 0, 1 or 2.

Specific examples of the radically polymerizable organic peroxide represented by Chemical Formula 2 include t-butylperoxyacryloyloxyethyl carbonate and t-amylperoxyacryloyloxyethyl carbonate. Tert-hexyl peroxyacryloyloxyethyl carbonate, 1,
1,3,3-tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate, t −
Butyl peroxymethacryloyloxyethyl carbonate
G, t-amyl peroxymethacryloyloxyethyl carbonate, t-hexylperoxymethacryloyloxyethyl carbonate, 1,1,3,3-tetramethylbutylperoxymethacryloyloxyethyl carbonate
G, cumyl peroxymethacryloyloxyethyl carbonate, p-isopropylcumylperoxymethacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate-carbonate, t-amyl Peroxyacryloyloxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate, 1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate
Bonnet, cumyl peroxyacryloyloxyethoxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate, t-
Butyl peroxymethacryloyloxyethoxyethyl carbonate, t-amylperoxymethacryloyloxyethoxyethyl carbonate, t-hexylperoxymethacryloyloxyethoxyethyl carbonate, 1,
1,3,3-tetramethylbutyl peroxymethacryloyloxyethoxyethyl carbonate, cumylperoxymethacryloyloxyethoxyethyl carbonate, p
-Isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate, t-butylperoxyacryloyloxyisopropylcarbonate, t-amylperoxyacryloyloxyisopropylcarbonate,
t-hexylperoxyacryloyloxyisopropyl carbonate, 1,1,3,3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate,
Cumyl peroxyacryloyloxyisopropyl carbonate, p-isopropylcumylperoxyacryloyloxyisopropyl carbonate, t-butylperoxymethacryloyloxyisopropyl carbonate, t-
Amyl peroxymethacryloyloxyisopropyl car
Bonnet, t-hexylperoxymethacryloyloxyisopropyl carbonate, 1,1,3,3-tetramethylbutylperoxymethacryloyloxyisopropyl carbonate, cumylperoxymethacryloyloxyisopropyl carbonate And p-isopropylcumylperoxymethacryloyloxyisopropylcarbonate.

Further, the compounds represented by the chemical formula 3 include:
t-butylperoxyallylcarbonate, t-amylperoxyallylcarbonate, t-hexylperoxyallylcarbonate, 1,1,3,3-tetramethylbutylperoxyallylcarbonate G, p-menthane peroxyallyl carbonate, cumyl peroxyallyl carbonate, t-butyl peroxymethallyl carbonate, t-amyl peroxymethallyl carbonate, t
Hexyl peroxymethallyl carbonate, 1,1,
3,3-tetramethylbutyl peroxymethallyl carbonate, p-menthane peroxymethallyl carbonate
G, cumyl peroxymethallyl carbonate, t-butyl peroxyallyloxyethyl carbonate, t-amyl peroxyallyloxyethyl carbonate, t-hexyl peroxyallyloxyethyl carbonate , T-butylperoxymetalaryloxyethyl carbonate, t-
Amyl peroxymetalaryloxyethyl carbonate, t-
Hexyl peroxymetalaryloxyethyl carbonate,
t-butylperoxyallyloxyisopropyl carbonate, t-amylperoxyallyloxyisopropylcarbonate, t-hexylperoxyallyloxyisopropylcarbonate, t-butylperoxymetalloxyisopropylcarbonate And t-amyl peroxymetalaryloxyisopropyl carbonate, t-hexylperoxymetalaryloxyisopropyl carbonate and the like.

Particularly preferred are t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyallylcarbonate, and t-butylperoxy. Methallyl carbonate.

The mixing ratio of the multi-phase structure graft copolymer (2) in the thermoplastic resin composition of the present invention is from 0.1 to 0.1%.
It is preferably 50% by weight, more preferably 0.5 to 30% by weight. If the amount of the multi-phase structure graft copolymer is less than 0.1% by weight, the coating property is insufficiently improved, and 50% by weight.
Exceeding the heat resistance is undesirably reduced.

Next, in the second invention, a thermoplastic elastomer (3) is blended with a thermoplastic resin composition comprising a thermoplastic resin (1) and a multi-phase structure graft copolymer (2). . This thermoplastic elastomer (3)
Improves the mechanical strength such as the impact resistance of the thermoplastic resin composition, and also improves the heat resistance.

Examples of the thermoplastic elastomer (3) include diene rubbers such as polybutadiene, styrene-butadiene copolymer, polyacrylonitrile-butadiene copolymer, polyisoprene, ethylene-α-olefin copolymer, ethylene-α- Non-diene rubber such as olefin-polyene copolymer, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, ethylene-propylene elastomer, styrene grafted ethylene-propylene elastomer, ethylene ionomer resin And hydrogenated styrene-isoprene block copolymer. These thermoplastic elastomers are 1
Species or a mixture of two or more can be used.

Among these thermoplastic elastomers (3), ethylene-propylene copolymer rubber (EPM) and ethylene-propylene-diene copolymer rubber are preferred in terms of impact resistance, gasoline resistance and surface appearance of molded articles. (EPDM)
Is preferred. More preferably, the Mooney viscosity (ML1 + 4
, 100 ° C) of 5 to 150.

From the viewpoint of mechanical properties and heat resistance, the total amount of the thermoplastic elastomer (3) is 1 in terms of the total amount of the thermoplastic resin (1) and the multi-phase graft copolymer (2).
1 to 300 parts by weight, more preferably 1 to 200 parts by weight, particularly preferably 1 to 300 parts by weight, per 100 parts by weight.
100 parts by weight. If the amount is less than 1 part by weight, the elasticity of the resin composition tends to be low, and if it exceeds 300 parts by weight, the heat resistance tends to decrease. In addition, thermoplastic elastomer (3)
If the compounding ratio of is within such a range, there is no possibility that the moldability is reduced.

Further, in the present invention, the total amount of the thermoplastic resin (1) and the multi-phase structure graft copolymer (2) is 1
200 parts by weight or less of the inorganic filler (4) may be added to 00 parts by weight. If the amount exceeds 200 parts by weight, the impact strength of the molded article is undesirably reduced. As the inorganic filler, specifically, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite,
Granular filler such as silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, mica, glass plate, sericite, pyrophyllite, aluminum free
Metal foils such as steel, flat or flaky fillers such as graphite,
Hollow filler such as shirasu balloon, metal balloon, glass balloon, pumice stone, mineral fiber such as glass fiber, carbon fiber, graphite fiber, whisker, metal fiber, silicone carbide fiber, asbestos, westonite Examples can be given. Examples of the shape of the inorganic filler include a powder, a particle, a plate, a scale, a hollow, a fiber, a needle, a sphere, and the like as described above.

Among them, calcium carbonate, barium sulfate,
Talc is preferred. Furthermore, mechanical properties, appearance of molded products,
Talc is preferred from the viewpoint of heat resistance. Talc may be generally commercially available, but particularly preferred is one having an average particle size of 1 to 4 μm. These inorganic fillers alone,
Alternatively, two or more kinds can be used.

On the surface of the inorganic filler (4), stearic acid, oleic acid, palmitic acid or a metal salt thereof, paraffin wax, polyethylene wax or a modified product thereof, organic silane, organic borane, organic titanate
It is preferable to perform a surface treatment using a metal or the like.

The thermoplastic resin composition of the present invention has a temperature of 1
It is manufactured by melting and mixing at 50-350 ° C. If the temperature is lower than 150 ° C., the melting is incomplete, the melt viscosity is high, the mixing becomes insufficient, and phase separation or delamination tends to appear in the molded product, which is not preferable. On the other hand, when the temperature exceeds 350 ° C., decomposition or gelation of the resin to be mixed easily occurs, which is not preferable.

As a method of melting and mixing, Banbury
It can be carried out by a commonly used kneading machine such as a mixer, a pressure kneader, a kneading extruder, a twin-screw extruder or a roll. In the present invention, further, an inorganic flame retardant such as magnesium hydroxide and aluminum hydroxide, an organic flame retardant such as a halogen type and a phosphorus type, a metal powder, an antioxidant, an ultraviolet ray inhibitor, and a lubricant within a range not departing from the gist of the invention. , A dispersing agent, a coupling agent, a foaming agent, a crosslinking agent, a coloring agent, and additives such as carbon black may be added.

In the present invention, the thermoplastic resin composition comprising the thermoplastic resin (1) and the multi-phase structure graft copolymer (2) or the resin composition containing the thermoplastic resin (3) and the thermoplastic resin (3) are as follows: Since it has excellent mechanical properties, moldability, impact resistance, coating film adhesion, and even paintability, it can be used for various applications. That is, the thermoplastic resin composition is molded into a molded article having a predetermined shape by an injection molding method, an extrusion molding method, or the like. The obtained molded article can be used, for example, for bumpers, moldings, mudguards, other electric products, building members and the like as automobile parts. Among them, it is particularly suitable for use as exterior parts such as bumpers, moldings, and mudguards for automobiles.

[0060]

According to the first aspect of the present invention, the multi-phase graft copolymer (2) is usually uniformly dispersed well in the thermoplastic resin (1) because the B segment constituting the graft copolymer controls the compatibility of the A segment. You. When the thermoplastic resin composition is molded by injection molding or the like, the thermoplastic resin (1) and the multiphase graft copolymer (2) have a melt viscosity in the vicinity of the surface of the molded article due to the melt viscosity of the thermoplastic resin (1). The copolymer (2) is oriented. Therefore, properties such as paintability and coating film adhesion are improved based on such improvements in compatibility and orientation.

In the second invention, a thermoplastic elastomer is blended with the thermoplastic resin composition of the first invention, and in addition to the function of the first invention, its elasticity improves mechanical properties such as impact resistance. Is achieved.

In the third invention, a resin molded article is obtained by molding the thermoplastic resin composition of the first or second invention into a predetermined shape by a molding method such as an injection molding method. The physical properties of the composition are effectively exhibited.

[0063]

EXAMPLES The present invention will be described more specifically with reference to the following Reference Examples, Examples and Comparative Examples. (Reference Example 1) (Production of multiphase graft copolymer (2A)) Into a stainless steel autoclave having a volume of 5 liters, 2500 g of pure water was added, and 2.5 g of polyvinyl alcohol was further used as a suspending agent. Was dissolved. 800 g of an ethylene-vinyl acetate copolymer "NUC3150" (trade name, manufactured by Nippon Unicar Co., Ltd., containing 20% vinyl acetate) was added thereto, and the mixture was stirred and dispersed. Separately, 1.5 g of benzoyl peroxide "Niper-B" (trade name, manufactured by NOF Corporation) as a polymerization initiator, and t-butylperoxymethacryloyloxyethyl carbonate as a radical polymerizable organic peroxide.
4 g of the carbonate was dissolved in 200 g of stearyl methacrylate as a vinyl monomer, and this solution was charged into the autoclave and stirred.

Next, the autoclave was heated to 60 to 65 ° C. and stirred for 2 hours to thereby polymerize the polymerization initiator, radically polymerizable organic peroxide and vinyl monomer with ethylene-vinyl acetate copolymer. Impregnated during coalescence. Next, after confirming that the total amount of the impregnated vinyl monomer, the radically polymerizable organic peroxide and the polymerization initiator is 50% by weight or more, the temperature is increased to 80 to 85 ° C, 4 at that temperature
The polymerization was completed by maintaining for a period of time, washed with water and dried to obtain a grafting precursor (A). This grafting precursor (A)
Of stearyl methacrylate polymer was extracted with tetrahydrofuran and gel permeation chromatography (G
PC), the number average degree of polymerization was 700.

Next, the grafting precursor (A) was subjected to a Labo Plastomill single screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.).
At 200 ° C. and a grafting reaction was carried out to obtain a thermoplastic resin having a multiphase structure (2A).

The multi-phase thermoplastic resin (2A) was observed with a scanning electron microscope “JEOL JSMT300” (trade name, manufactured by JEOL Ltd.).
It was a thermoplastic resin having a multiphase structure in which true spherical resins of 3 to 0.4 μm were uniformly dispersed.

At this time, the grafting efficiency of the stearyl methacrylate polymer was 75% by weight. (Reference Examples 2 to 8) (Multiphase structure graft copolymer (2B to
Production of 2H)) In the same manner as in Reference Example 1, the type of the copolymer of the nonpolar α-olefin monomer and the polar vinyl monomer and the type of the vinyl monomer were changed to obtain a polyphase graft copolymer. Polymer (2B-2
H) was obtained. In addition, a polyphase graft copolymer (2I to 2M) was obtained from a (co) polymer consisting only of a non-polar α-olefin monomer and a vinyl monomer.

Table 1 shows the charged composition of the multiphase graft copolymer and the polymerization results. The abbreviations in Table 1 indicate the following copolymers and monomers. EVA (NUC3150): Ethylene-vinyl acetate copolymer, containing 20% vinyl acetate (trade name: manufactured by Nippon Unicar Co., Ltd.) EGMA: Ethylene-glycidyl methacrylate copolymer, containing 15% glycidyl methacrylate E / EA / MAN : Ethylene-ethyl acrylate-maleic anhydride copolymer, containing 15% ethyl acrylate, 3% maleic anhydride EVAL: ethylene-vinyl alcohol copolymer, containing 20% vinyl alcohol EAA: ethylene-acrylic acid copolymer, acrylic Acid 1
5% EVA (V270): ethylene-vinyl acetate copolymer, 15% vinyl acetate, Lexpearl V-
270: (trade name, manufactured by Nippon Oil Co., Ltd.) EEA: ethylene-ethyl acrylate copolymer, containing 25% of ethyl acrylate (trade name, manufactured by Nippon Oil Co., Ltd.
Nisseki Lexlon EEA, A4250) EMA: Ethylene-methyl acrylate copolymer, containing 12% of methyl acrylate (trade name, manufactured by Nippon Oil Co., Ltd.)
Nisseki Lexpearl, RB5120) PP: polypropylene, PP / PE: propylene-ethylene copolymer, SMA: stearyl methacrylate, S
t: styrene, MMA: methyl methacrylate, BM
A: butyl methacrylate, LMA: lauryl methacrylate, SA: stearyl acrylate, HEMA: 2
-Hydroxyethyl methacrylate, MAA: methacrylic acid

[0069]

[Table 1]

(Examples 1 to 10) Propylene polymer (1) “Nisseki Polypro J630G” (trade name, manufactured by Nippon Petrochemical Co., Ltd.) and the multiphase structure graft obtained in Reference Examples 1 to 7 The polymers (2A) to (2G) were melt-mixed at the ratios shown in Table 2.

The melt viscosities of the graft copolymer and the polypropylene were measured by "Capillograph PH1B" manufactured by Toyo Seiki Co., Ltd.
It measured using. That is, a thermoplastic resin was filled into a cylinder heated to a constant temperature while paying attention so that air bubbles did not enter, and then the melt viscosity of the resin was measured while applying a load.

In the melt mixing method, pellets of each resin were dry-blended, and then supplied to a coaxial twin-screw extruder having a cylinder diameter of 230 ° C. and a screw diameter of 30 mm, followed by granulation after extrusion. . A test piece was prepared by injection molding using the granulated resin. The size of the test piece is as follows.

Izod impact test piece 13 mm × 65 mm × 6 mm
(With notch) Load deflection temperature test piece 13mm × 130mm × 6mm Coating adhesion test piece 45mm × 90mm × 4mm The test method is as follows. (1) Izod impact value (with notch): JIS K7110 (2) Deflection temperature under load: JIS K7207 (3) Coating adhesion: A polyolefin primer was applied to the test piece, and an acrylic paint was applied thereon. Thereafter, eleven vertical and horizontal cuts at 1 mm intervals are made by a knife until reaching the material, and 100 squares each having a side length of 1 mm are formed in a grid shape. (Nichiban Co., Ltd.) was adhered, and it was represented by the number of squares remaining without being peeled off when it was instantaneously peeled off. (4) Gasoline resistance: A polyolefin-based primer is applied to the test piece, and an acrylic-based paint is applied thereon.
After immersion in regular gasoline for 30 minutes, the surface condition was examined.

: No abnormality in the coating film, Δ: Partial peeling of the coating film, ×: Peeling of the entire coating film (5) Appearance: Simulated bumper (length 460 mm × width 120 mm ×
Height 56mm, bumper-4 ribs on the back, 3m thick
m) was molded and its appearance (flow mark, ie, the presence or absence of a pattern caused by uneven film thickness due to repelling of the bumper surface) was examined.

Table 2 shows the results.

[0076]

[Table 2]

As shown in Table 2, the thermoplastic resin compositions of Examples 1 to 10 comprising a polypropylene and a graft copolymer showed the Izod impact value, load deflection,
It shows good performance in all of coating film adhesion, gasoline resistance and appearance. Therefore, the resin molded product has excellent coating film adhesion and impact resistance while maintaining the characteristics of the thermoplastic resin such as excellent mechanical properties and moldability. Moreover,
Since no flow mark is generated in appearance, it is excellent in paintability. Also, when the blending amount of the graft copolymer is increased, the impact strength is improved (Examples 1 to 3). (Examples 11 to 20) Propylene-based polymer (1) "Nisseki Polypro J630G" (trade name, Nippon Petrochemical Co., Ltd.)
), The multiphase graft copolymers (2A) to (2C) obtained in Reference Examples 1 to 3, the grafted precursor obtained in Reference Example 1, and a thermoplastic elastomer (3) “EPO2P” (product) Table 3 shows an example of the blending of Nippon Synthetic Rubber Co., Ltd.).

[0078]

[Table 3]

As shown in Table 3, in the thermoplastic resin compositions of Examples 11 to 20 in which the polypropylene, the graft copolymer, and the thermoplastic elastomer were further blended, the Izod impact value, the load deflection, and the coating adhesion It shows good performance in all of properties such as water resistance, gasoline resistance and appearance. Further, when the blending amount of the thermoplastic elastomer is increased, the impact strength is improved (Examples 15 to 20). (Examples 21 to 30) Table 4 shows examples in which talc was further added as an inorganic additive (4) to the resin composition. The talc in Table 4 is "LMS-200" (trade name, manufactured by Fuji Talc Industries Co., Ltd.), and the numbers represent parts by weight based on 100 parts by weight of the resin component.

[0080]

[Table 4]

As shown in Table 4, in the thermoplastic resin compositions of Examples 21 to 30 to which polypropylene, the graft copolymer, the thermoplastic elastomer, and talc were further added as an inorganic additive, the impact strength and Load deflection is improved. (Comparative Examples 1 to 10) Examples in which the multiphase structure graft copolymers (2A) to (2H) of the above examples were not used, melt viscosity of the propylene-based polymer (1) / multilayer structure graft copolymer (2) Table 5 shows examples in which the ratio was less than 0.05. In Table 5, polypropylene means "Nisseki Polypro J630".
G) was mixed with 0.05% by weight of "Perbutyl P" (trade name, manufactured by NOF CORPORATION) and kneaded at 200 ° C to reduce the molecular weight and reduce the melt viscosity.
Other abbreviations in Table 5 are the same as those in Table 1 described above.

[0082]

[Table 5]

As shown in Table 5, when a normal copolymer other than the graft copolymer was blended with polypropylene (Comparative Examples 1 to 8), the performance such as coating film adhesion was reduced. Further, even in the case of a thermoplastic resin composition in which a graft copolymer is blended with polypropylene, when the melt viscosity ratio of the polypropylene and the graft copolymer is less than 0.05 (Comparative Examples 9 and 10), the coating film adheres. In addition, the impact strength is reduced. (Examples 31 to 36) In Example 12, the polypropylene was replaced with a polyamide resin "UBE nylon 1022B".
(Trade name of Ube Industries, Ltd.), aromatic polyester resin "Duranex 2002" (trade name of Polyplastics Co., Ltd.), polyoxymethylene resin "Duracon M90" (polyplastics Co., Ltd.) Table 6 shows an example in which polyphenylene sulfide resin “Fortron KPS” (trade name of Kureha Chemical Industry Co., Ltd.) and polyethylene “Sumikacene G401” (trade name of Sumitomo Chemical Co., Ltd.) were used. In Table 6, NB indicates that the test piece did not break.

[0084]

[Table 6]

As shown in Table 6, a thermoplastic resin composition (Examples 31 to 36) was prepared by using various crystalline resins and non-polar α-olefin resins and blending them with a graft copolymer and a thermoplastic elastomer. ) Is the Izod impact value,
It shows good performance in load deflection, coating film adhesion, gasoline resistance and appearance. (Comparative Examples 11 to 15) Table 7 shows examples in which the multiphase structure graft copolymer was not added in Examples 31 to 36.

[0086]

[Table 7]

As shown in Table 7, various crystalline resins and non-polar α-olefin resins were used, and thermoplastic elastomers were blended in these resins, but the thermoplastic resin composition was not blended with the graft copolymer. In Comparative Examples 11 to 15, the performance such as coating film adhesion is reduced. (Comparative Examples 16 to 20) A multi-phase structure graft copolymer (2I to 2M) synthesized using a (co) polymer consisting of only a non-polar α-olefin monomer was added to polypropylene and a thermoplastic elastomer. Examples are shown in Table 8.

[0088]

[Table 8]

As shown in Table 8, in Comparative Examples 16 to 20, the graft copolymer consisting of only a non-polar α-olefin monomer was used as the graft copolymer, and thus the performance such as coating film adhesion was improved. Decreased.

[0090]

According to the thermoplastic resin composition of the first invention, excellent mechanical properties, moldability and other characteristics of the thermoplastic resin are ensured, and excellent coating film adhesion and impact resistance are obtained. It has an excellent effect of having weather resistance and exhibiting good paintability.

According to the second aspect, in addition to the effects of the first aspect, an excellent effect that mechanical properties such as impact resistance can be improved. According to the third invention, a resin molded product can be easily molded into a predetermined shape from the thermoplastic resin composition of the first invention or the second invention, and the obtained resin molded product has the thermoplastic resin composition. The effect can be exhibited sufficiently, and particularly, it can be suitably used as an exterior component such as an automobile bumper.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 23/02-23/16 C08L 51/06 C08L 101/00-101/16

Claims (3)

(57) [Claims] (1) at least one kind of thermoplastic resin selected from the group consisting of a non-polar α-olefin resin and a crystalline resin, (2) a non-polar α-olefin monomer and a polar vinyl (A)
Segment) and a vinyl polymer or copolymer (B segment) formed from at least one vinyl monomer, wherein one segment forms a dispersed phase as fine particles in the other segment. And a melt viscosity ratio of the component (1) and the component (2) is 0.05 or more. 2. A thermoplastic resin composition comprising the thermoplastic resin composition according to claim 1 and a thermoplastic elastomer. 3. A resin molded product obtained by molding the thermoplastic resin composition according to claim 1 into a predetermined shape.