JP3000664B2 - Surface treatment method and coating method for resin composition molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel surface treatment method and a coating method for a resin composition molded article which can be used as a molded article, sheet or film by injection molding or extrusion molding. Things.

More specifically, at least one thermoplastic resin selected from a polypropylene resin and a polyamide resin, a polyphenylene ether resin, a mixture of a polyphenylene ether resin and a styrene resin, a graft copolymer of a polyphenylene ether resin and styrene, and a saturated polyester resin. The present invention relates to a surface treatment method and a coating method for a novel resin composition molded article having excellent physical property balance and appearance obtained by blending a compatibilizer with the above.

<Conventional technology> Polypropylene has excellent properties such as moldability, toughness, water resistance, gasoline resistance, and chemical resistance, and is low in specific gravity and inexpensive. It has been widely used as a sheet.

However, polypropylene has difficulties or needs improvement in heat resistance, rigidity, impact resistance, scratch resistance, paintability, adhesiveness, printability, etc., and these are obstacles to cultivating new practical applications. I have.

Among them, the improvement of paintability, adhesiveness, printability, etc. is described in, for example, Japanese Patent Publication No.
As described in JP-A-8-49736 and the like, a direction in which part or all of polypropylene is graft-modified with an unsaturated carboxylic acid such as maleic anhydride or an anhydride thereof has been proposed. However, even when such a modified polypropylene is used, it does not essentially improve the impact resistance, heat resistance, rigidity and other physical properties.

Further, in order to further improve the compatibility between the polypropylene, the adhesive and the coating material, a medium called a primer composed of, for example, chlorinated polypropylene and toluene, which are known as typical compositions, is usually used in the middle. I have.

However, since the primer itself is expensive and the addition of one step increases the final product cost, further improvement is desired.

Surface preparation for painting, printing and bonding includes:
Sand blasting, chromic acid mixture treatment, flame treatment, corona discharge treatment, plasma treatment, surface functional grouping method, surface light grafting method, etc. have been proposed, but none of these methods has achieved satisfactory results.

Sandblasting is a method of roughening the surface of a material by colliding the granular abrasive with the material at a high speed. However, there are problems such as the work environment and the product being stained by the granular abrasive. Need to be washed with water. Also,
There is a problem that the surface becomes opaque due to the treatment, and it is impossible to remove the abrasive material that has cut into the surface.

The chromic acid mixture treatment is a method in which a chromic acid mixture (75 parts of potassium dichromate, 120 parts of water, 1500 parts of concentrated sulfuric acid) is heated to about 100 ° C, and the object to be treated is immersed for about 5 minutes. However, there is a problem that the burden required for detoxifying the processing waste liquid is large.

Flame treatment is a method of treating the surface of a molded article with a gas oxidizing flame (1000 to 2500 ° C) mixed with excess air. However, deformation and melting may occur due to heat.

The corona discharge treatment is a method in which a film or a film-like object is passed through a gap between an electrode and a metal roll and a high voltage is applied to perform treatment.

The plasma treatment is a method in which low-temperature plasma is applied to the surface of a plastic to perform a treatment. The surface is chemically changed by an ionized gas and ultraviolet light, and oxygen or air plasma is used. The disadvantage of this method is that the cost of the processing equipment is large.

As a method for imparting a surface functional group, for example, there is a method of irradiating ultraviolet rays in a chlorine gas and then treating with an alkali. However, it is a problem because extremely dangerous chlorine gas is used.

The surface photografting method includes, for example, a method in which benzophenone is kneaded into a polypropylene film and photografting polymerization of acrylamide is performed in an atmosphere in which oxygen is blocked. The drawback is that the processing steps are complicated when economics are taken into account.

As described above, these methods have various problems. For this reason, the development of new treatment methods has become a major technical issue.

On the other hand, polyamide resin, polyphenylene ether resin,
Saturated polyester resins are widely used in the fields of automobile parts, electric and electronic parts, etc. as engineering resins with characteristics such as heat resistance, rigidity, strength, and oil resistance. Further improvements in water resistance, chemical resistance and the like are desired. Further, it has an essential disadvantage that it has a higher specific gravity and a higher price than polyolefin.

<Problems to be Solved by the Invention> Under such circumstances, a polypropylene resin selected from polypropylene, modified polypropylene or modified polypropylene / polypropylene composition and at least one engineering resin selected from polyamide resin, polyphenylene ether resin, and saturated polyester resin If a resin composition having the characteristics of both a polypropylene-based resin and an engineering resin can be obtained by blending, a wide range of new applications is expected.

However, conventionally, polypropylene resins and these engineering resins have been regarded as a combination with extremely poor compatibility and dispersibility. If they are simply mixed, the field variation effect of the molten polymer will be remarkable, and the stable take-up of the extruded strand will not be possible. It is almost impossible, and the workability of molding is remarkably reduced.

Injection moldings exhibit extreme non-uniformity, have poor appearance due to the occurrence of flow marks, and can only be used for automobile parts, electric / electronic parts, etc., which are not practically usable.

In addition, the mechanical properties of molded products made from a mixture of polypropylene resin and these engineering resins, especially impact resistance, tensile elongation, etc., usually show values lower than those expected from the additive properties of each individual material. There were many problems.

According to the method exemplified in JP-A-61-64741, a polypropylene and a polyamide which are originally incompatible with each other are mixed with a polypropylene-based resin and a polyamide resin selected from a modified polypropylene or a modified polypropylene / polypropylene composition and an epoxy group-containing polyamide. It is possible to dissolve and disperse by blending a polymer. Moldability, rigidity, heat resistance, impact resistance, scratch resistance, oil resistance, chemical resistance,
It is possible to produce a thermoplastic resin composition that has a good balance of physical properties such as water resistance and has excellent uniformity and smoothness in appearance.

An object of the present invention is to provide a method for surface-treating a molded article of a thermoplastic resin composition having excellent properties such as heat resistance and impact resistance and extremely excellent paintability, adhesiveness and printability, and a method for coating the molded article. Is to provide.

<Means for Solving the Problems> To achieve the above object, as a result of intensive studies, it has been found that the surface of a thermoplastic resin composition molded article having good physical property balance, uniform appearance and excellent smoothness is 300 nm or less. By irradiating ultraviolet light having the main wavelength to the region (1), it was found that the surface properties of the molded article of the thermoplastic resin composition were significantly improved, and the present invention was reached.

That is, the present invention relates to a polyamide resin, a polyphenylene ether resin, a mixture of a polyphenylene ether resin and a styrene resin, a polyphenylene ether resin, a polyamide resin, a polyphenylene ether resin, 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition. 100 parts by weight of a resin composition (I) composed of 95 to 0.5% by weight of at least one thermoplastic resin (B) selected from a graft copolymer of styrene and a saturated polyester resin; As a compatibilizer for improving the compatibility of the thermoplastic resin (B),
At least one compatibilizer selected from dicarboxylic acid compounds or derivatives thereof having two or more carboxyl groups in the molecule, diamine compounds or derivatives thereof having two or more nitrogen atoms in the molecule, and epoxy group-containing copolymers; (II) A method for surface treating a resin composition molded article, comprising irradiating a molded article obtained by molding a resin composition comprising 0 to 30 parts by weight with an ultraviolet ray having an irradiation wavelength in a region of 300 nm or less. And a method for coating the molded article, which is further coated with a urethane paint or the like.

 Hereinafter, the configuration of the present invention will be specifically described.

[1] Basic resin [A] Polypropylene resin The polypropylene resin (A) used in the present invention is a resin selected from a modified polypropylene and a modified polypropylene / polypropylene composition.

Here, polypropylene is crystalline polypropylene, and includes a block copolymer or a random copolymer obtained by copolymerizing propylene with an α-olefin such as ethylene and butene-1 in addition to a homopolymer of propylene. Modified polypropylene refers to 0.05 to 20% by weight, preferably 0.1 to 20% by weight of unsaturated carboxylic acid or anhydride thereof based on the homopolymer or copolymer of propylene.
Graft-modified in the range of 1010% by weight.

The polypropylene resin (A) preferably has a melt index of 0.1 to 100 g / 10 min, particularly 0.5 to 40 g / 10 min.

The propylene homopolymer, block or random copolymer can be obtained by, for example, reacting in the presence of a catalyst in combination with titanium trichloride and an alkylaluminum compound, which is usually called a Ziegler-Natta type catalyst.

Examples of the graft monomer in the modified polypropylene graft-modified with an unsaturated carboxylic acid or an anhydride thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride. Of these, maleic anhydride is particularly preferred.

Various known methods can be employed for grafting the graft monomer onto the polypropylene.

For example, polypropylene is mixed with a graft monomer and a radical initiator, melt-kneaded in an extruder, and grafted. Dissolve polypropylene in an organic solvent such as xylene, add a radical generator under a nitrogen atmosphere, and heat with stirring. A method of reacting, cooling after the reaction, washing and filtering, and drying to obtain a grafted polypropylene, a method of irradiating the polypropylene with ultraviolet light or radiation in the presence of a graft monomer, or a method of bringing the polypropylene into contact with oxygen or ozone are used.

(B) Thermoplastic resin (engineering resin) Polyamide resin The polyamide resin in the present invention is a polyamide obtained by polycondensation of a lactam having three or more rings, a polymerizable ω-amino acid, a dibasic acid and a diamine. Can be. Specifically, polymers such as ε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and metaxylylenediene A polymer obtained by polycondensation of a diamine such as an amine with a dicarboxylic acid such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid, glutaric acid, or a copolymer thereof is included.

Specific examples include aliphatic polyamides such as polyamide 6, polyamide 6.6, polyamide 6.6, polyamide 6,10, polyamide 11, polyamide 12, polyamide 612, polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, xylene. Examples include aromatic polyamides such as group-containing polyamides, and these can also be used as a mixture or copolymer of two or more.

Polyphenylene ether resin The polyphenylene ether resin in the present invention is represented by the general formula (Wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are hydrogen, a halogen atom,
It is selected from a hydrocarbon group or a substituted hydrocarbon group, one of which is necessarily a hydrogen atom. The phenolic compound is a polymer obtained by oxidatively polymerizing one or more of the phenolic compounds represented by the formula (2) with oxygen or an oxygen-containing gas using an oxidation coupling catalyst.

Specific examples of R ₁ , R ₂ , R ₃ , R ₄ , and R _{5 in} the above general formula include hydrogen, chlorine, bromine, fluorine, iodine, methyl,
Ethyl, n- or iso-propyl, pri-, sec- or t
-Butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl, allyl and the like.

Specific examples of the above general formula include phenol, o-, m-,
Or p-cresol, 2,6-, 2,5-, 2,4-, or 3,5
-Dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3,6
-Or 2,4,6-trimethylphenol, 3-methyl-6
-T-butylphenol, thymol, 2-methyl-6-allylphenol and the like. Further, phenolic compounds other than the above general formula, for example, bisphenol-A,
Copolymerization of a polyvalent hydroxy aromatic compound such as tetrabromobisphenol-A, resorcin, hydroquinone, and novolak resin with the above general formula may also be used.

Preferred among these compounds are homopolymers of 2,6-dimethylphenol or 2,6-diphenylphenol and a large part of 2,6-dimethylphenol and a small part of 3-methyl-6-t- Butylphenol or
Copolymers of 2,3,6-trimethylphenol are exemplified.

More preferred is poly (2,6-dimethyl-1,4-phenylene) ether, which is a homopolymer of 2,6-dimethylphenol.

The oxidative coupling catalyst used for oxidatively polymerizing the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used. For example, typical examples thereof include cuprous chloride-triethylamine, cuprous chloride-pyridine and the like, catalysts composed of cuprous salts and tertiary amines, cupric chloride-pyridine-potassium hydroxide and the like. Catalyst consisting of manganese salts such as manganese chloride-ethanolamine, manganese acetate-ethylenediamine and primary amines, manganese chloride-sodium methylate, manganese chloride A catalyst comprising a combination of a manganese salt such as sodium phenolate and an alcoholate or a phenolate; and a catalyst comprising a combination of a cobalt salt and a tertiary amine.

The reaction temperature of oxidative polymerization to obtain polyphenylene ether is higher than 40 ℃ (high temperature polymerization) and 40 ℃
It is known that there is a difference in physical properties and the like from the case where the polymerization is performed below (low-temperature polymerization), but in the present invention, either high-temperature polymerization or low-temperature polymerization can be employed.

Further, in the present invention, a graft copolymer of polyphenylene ether resin and styrene or a mixture of polyphenylene ether and styrene resin can be used. These production methods are described in JP-B-47-47.
No. 862, No. 48-12197, No. 49-5623, No. Sho
As disclosed in JP-B-52-38596 and JP-B-52-30991, a method in which a styrene monomer and / or another polymerizable monomer is subjected to an organic peroxide graft polymerization in the presence of polyphenylene ether. Or a method of melt-kneading the above-mentioned polyphenylene ether resin, styrene resin and, if necessary, a radical initiator, as disclosed in JP-A-52-142799.

The styrenic resin in the present invention is specifically a polymer comprising one or more polymerized units selected from styrene, α-methylstyrene, p-methylstyrene and the like, and specifically, polystyrene, rubber Reinforced polystyrene,
Examples thereof include poly-α-methylstyrene, poly-p-methylstyrene, styrene-acrylonitrile copolymer and the like.

Saturated Polyester Resin The saturated polyester resin in the present invention comprises a dicarboxylic acid component and a diol component in which at least 40 mol% of the dicarboxylic acid component is terephthalic acid. The dicarboxylic acid components other than the terephthalic acid include adipic acid and sebacic acid. With 2 carbon atoms, such as dodecanedicarboxylic acid
Or a mixture of aromatic dicarboxylic acids such as aliphatic dicarboxylic acid, isophthalic acid, and naphthalenedicarboxylic acid, or alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Examples thereof include aliphatic glycols such as 3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol, and alicyclic glycols alone or in a mixture.

Among these saturated polyester resins, the effects of the present invention can be more desirably exhibited particularly in the case of polybutylene terephthalate or polyethylene terephthalate. These saturated polyester resins use o-chlorophenol as a solvent and have an intrinsic viscosity of 0.5 to 0.3 dl /
It is preferably in the range of g, and even if a saturated polyester resin having a viscosity outside this range is used, the desired mechanical strength cannot be expected.

[2] Compatibilizer (II) Unsaturated carboxylic acid compound or derivative thereof The unsaturated carboxylic acid compound or derivative thereof used in the present invention includes, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid , End-
Cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid, bicyclo (2,2,2) oct-5-ene-2,3-dicarboxylic acid, 4-methylcyclohexa-4 -Ene 1,2 dicarboxylic acid, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid, bicyclo (2,2,1) oct-7-
Unsaturated carboxylic acids such as ene-2,3,5,6-tetracarboxylic acid, 7-oxabicyclo (2,2,1) hept-5-ene-2,3 dicarboxylic acid, and unsaturated carboxylic acids; Derivatives include acid anhydrides, esters, amides, imides, and metal salts, such as maleic anhydride, itaconic anhydride, citraconic anhydride, endo-cis-bicyclo (2,2,
1) -5-heptene-2,3-dicarboxylic acid, anhydride, monoethyl maleate, monomethyl fumarate, monomethyl itaconate, monoethyl fumarate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylamide, acrylamide Methacrylamide, maleic monoamide, maleic diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide,
Fumaric acid monoamide, fumaric acid diamide, fumaric acid-N
Monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N
-Dibutylamide, maleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate,
Examples thereof include potassium acrylate and potassium methacrylate.

Of these, maleic anhydride is most preferably used.

Amine compounds or their derivatives Amines containing two or more nitrogen atoms in the molecule include hexamethylenediamine, hexamethylenetetramine, polyalkylenepolyamine, phenylenediamine, 4,4'-diaminodiphenyl compound, and m-xylenediamine. And aniline, N-alkyl and toluidine derivatives of phenylanilines.

Urea or its derivative, urea is CO (NH ₂ ) ₂ and its derivative is methyl urea, sym-diethyl urea, ethyl urea, sym-dimethyl urea, unsym-diethyl urea, acetyl urea, acetyl methyl urea, sym-ethyl phenyl urea,
Phenylurea, sym-diphenylurea, benzylurea, tetraphenylurea, benzoylurea, p-ethoxyphenylurea, ethyleneurea, thiourea, allylthiourea, sym
-Dimethylthiourea, sym-diethylthiourea, sym-diphenylthiourea, phenylthiourea, benzylthiourea, s-benzylisothiourea, benzoylthiourea and the like.

Epoxy group-containing copolymer The epoxy group-containing copolymer in the present invention is a copolymer comprising an unsaturated epoxy compound and one or more ethylenically unsaturated compounds.

The composition ratio of the epoxy group-containing copolymer is not particularly limited, but it is desirable that the unsaturated epoxy compound is copolymerized at 0.1 to 50% by weight, preferably 1 to 30% by weight.

The unsaturated epoxy compound is a compound having an unsaturated group copolymerizable with an ethylenically unsaturated compound in the molecule and an epoxy group.

For example, unsaturated glycidyl esters and unsaturated glycidyl ethers represented by the following general formulas (1) and (2) are exemplified.

(R is a hydrocarbon group having 2 to 18 carbon atoms having an ethylenically unsaturated bond.) (R is a hydrocarbon group having 2 to 18 carbon atoms which has an ethylenically unsaturated bond, X is -CH ₂ -O-, or It is. Specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, acryl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether and the like.

Ethylenically unsaturated compounds are olefins and C2
Vinyl esters of saturated carboxylic acids having 1 to 6 carbon atoms,
And esters of a saturated alcohol component with acrylic acid or methacrylic acid, maleic esters, methacrylic esters and fumaric esters, vinyl halides, styrenes, nitriles, vinyl ethers and acrylamides. Can be

Specifically, ethylene, propylene, butene-1, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, diethyl maleate, diethyl fumarate,
Examples thereof include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, isobutyl vinyl ether, and acrylamide. Of these, ethylene is particularly preferred.

Epoxy group-containing copolymers can be made by various methods. Any of a random copolymerization method in which the unsaturated epoxy compound is introduced into the main chain of the copolymer and a graft copolymerization method in which the unsaturated epoxy compound is introduced as a side chain of the copolymer can be employed. Specifically, the unsaturated epoxy compound and ethylene are copolymerized in the presence of a radical generator at 500 to 4,000 atm and 100 to 300 ° C in the presence or absence of a suitable solvent or chain transfer agent. Method, a method in which an unsaturated epoxy compound and a radical generator are mixed with polypropylene and melt-grafted and copolymerized in an extruder, or an unsaturated solvent such as water or an organic solvent is used for the unsaturated epoxy compound and the ethylenically unsaturated compound. And a method of copolymerizing in the presence of a radical generator.

[3] Resin composition Rubber-like substance (IV), modified rubber-like substance (V) In the present invention, the rubber-like substance (IV) used for the purpose of improving impact resistance, particularly low-temperature impact resistance, is an ethylene-based substance. Polymer rubber, propylene butene rubber, isoprene butylene rubber, polyisoprene, polybutadiene, styrene block copolymers such as styrene butadiene rubber, styrene butadiene styrene block copolymer,
Partially hydrogenated styrene butadiene block copolymer, styrene isoprene block copolymer, partially hydrogenated styrene isoprene block copolymer, etc., linear low-density polyethylene, etc., or a mixture thereof are used.

Examples of the ethylene-based copolymer rubber include ethylene-propylene copolymer rubber (hereinafter abbreviated as EPM) and ethylene-propylene-nonconjugated diene copolymer rubber (hereinafter referred to as EPM).
Abbreviated as EPDM. ), Ethylene-α-olefin-non-conjugated diene copolymer rubber, ethylene-vinyl acetate copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene -Ethyl (meth) acrylate copolymer, ethylene-butyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid or its partial metal salt copolymer, ethylene- (meth) acrylic acid- (meth) Various ethylene copolymer rubbers such as an acrylate copolymer, an ethylene-vinyl alcohol copolymer, an ethylene-vinyl acetate-vinyl alcohol copolymer, and an ethylene-styrene copolymer can be used. These ethylene copolymer rubbers may be used as a mixture of two or more.
It is also possible to use a mixture with low-density polyethylene and high-density polyethylene having good compatibility with these ethylene copolymer rubbers.

As the modified rubber-like substance (V), an unsaturated carboxylic acid or a derivative thereof, or an unsaturated carboxylic acid or a derivative thereof and an unsaturated monomer may be added to the rubber-like substance (IV) by radical initiation, if necessary. It can be obtained by a method of graft copolymerization by coexisting an agent or a method of directly copolymerizing an unsaturated carboxylic acid or its derivative in the main chain of an α-olefin in the presence of a polymerization initiator and a catalyst.

Ethylene copolymer rubber and styrene-based block copolymer are preferably used as the rubber-like substance as a raw material of the rubber-like substance (IV) and the modified rubber-like substance (V).

Among the ethylene copolymer rubbers, an ethylene-α-olefin copolymer rubber and an ethylene-α-olefin-nonconjugated diene copolymer rubber are particularly preferable. As the ethylene-α-olefin copolymer rubber, ethylene and other α-olefins such as propylene, 1-butene, 1-pentene,
-Hexene, 4-methyl-1-pentene, 1-octene and the like, or terpolymer rubbers such as ethylene-propylene-1-butene copolymer and the like. Polymer rubber and ethylene-1-butene copolymer rubber are preferably used. Also, ethylene-α-olefin-non-conjugated diene copolymer rubber can be used, but it is preferable that the non-conjugated diene content in the raw rubber is 3% by weight or less. If the non-conjugated diene content exceeds 3% by weight, gelation occurs during kneading, which is not preferable.

The ethylene content in the ethylene-α-olefin copolymer rubber is 15 to 85% by weight, preferably 40 to 80% by weight.
That is, highly crystalline copolymers with an ethylene content of more than 85% by weight are difficult to process under normal rubber molding conditions, and those with an ethylene content of less than 15% by weight have an increased glass transition temperature (Tg) and are rubbery. It is not preferable because properties are lost.

The number average molecular weight of the ethylene-α-olefin copolymer rubber is preferably one that can be kneaded in an extruder, and is 10,000 to 100,000. If the molecular weight is too small, handling when feeding to an extruder is difficult, and if the molecular weight is too large, the fluidity becomes small and processing is difficult.

Also, the molecular weight distribution of the ethylene-α-olefin copolymer rubber is not particularly limited, and any copolymer rubber having various molecular weight distributions, such as monomodal type and dimodal type, which are usually manufactured and marketed, can be used. Can be used.

Q value of molecular weight distribution (weight average molecular weight / number average molecular weight)
Is preferably 1 to 30, more preferably 2 to 20.

That is, the copolymer rubber is a copolymer rubber produced by using a so-called Ziegler-Natta catalyst, which is a usual production catalyst. Are used in combination. Examples of the aluminum compound include alkyl aluminum sesquichloride,
Trialkylaluminum, dialkylaluminum monochloride, or a mixture thereof is used. As the vanadium compound, vanadium oxytrichloride, vanadium tetrachloride or VO (OR ⁸ ) _q X _3-q (0 <q
≦ 3, R ⁸ may be a vanadate compound represented by a linear, branched or cyclic hydrocarbon having 1 to 10 carbon atoms.

Among the styrene block copolymers, a partially hydrogenated styrene butadiene block copolymer is particularly preferred.
The partially hydrogenated styrene-butadiene block copolymer is produced by partially hydrogenating a styrene-butadiene block copolymer, and its production and production method will be described below.

As a partially hydrogenated styrene-butadiene block copolymer, the block copolymer rubber has a number average molecular weight of 10,000.
-1,000,000, preferably 20,000-300,000, and the number average molecular weight of the unsaturated aromatic polymer block A in the block copolymer rubber is 1,000-200,000, preferably 2,000-10,000.
The number average molecular weight of the conjugated diene polymer block B is 1,000 to 200,000, preferably 2,000 to 100,000.
The weight ratio of the unsaturated aromatic polymer block A to the conjugated diene polymer B is 2/98 to 60/40, preferably 10/90 to 40/60.

Many methods have been proposed for the production of block copolymer rubbers.
According to the method described in JP-A-40-23798, a block copolymer rubber of an unsaturated aromatic hydrocarbon and a diene hydrocarbon can be obtained by subjecting a lithium catalyst or a Ziegler-type catalyst to block polymerization in an inert solvent. it can.

 These block copolymer rubber hydrogenation treatments are, for example,
Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 63-6636,
Inert solution was obtained by the method described in
It is carried out in a medium in the presence of a hydrogenation catalyst. This hydrogenation
The percentage is at least 50% of the polymer block B, preferably
80% or more, aromatic unsaturation in polymer block A
Less than 25% of the bonds are nuclear hydrogenated. In this way,
Or fully hydrogenated block copolymers are available from US
Clayton from Ell Chemical -G (KRATON -G)
It is typically marketed under the trade name of.

In the method for producing the modified rubber-like substance (V), various known methods can be adopted as a method for graft-copolymerizing a graft monomer with a rubber-like substance as a raw material.

For example, a method in which a rubber-like material as a raw material, a graft monomer and a radical initiator are mixed and melt-kneaded in a melt-kneading apparatus for grafting. A radical initiator is added to the reaction mixture, and the mixture is heated and reacted under stirring. After the reaction, cooling, washing, filtration, and drying are performed to obtain a grafted ethylene copolymer rubber. In addition, in the presence of a graft monomer in the ethylene copolymer rubber And a method of contacting with oxygen or ozone.

In consideration of economy, a method of melt-kneading in a melt-kneading apparatus and graft-copolymerizing is most preferably used.

In the present invention, the modified rubber-like substance (V) is used in the presence of an unsaturated carboxylic acid or a derivative thereof and, if necessary, a radical initiator, or an unsaturated carboxylic acid or a derivative thereof. 200 to 2 in the presence of a saturated aromatic monomer and optionally a radical initiator
It can be obtained by melt-kneading using an extruder, a Banbury mixer, a kneader or the like at a temperature of 80 ° C, preferably 230 to 260 ° C and a residence time of 0.2 to 10 minutes, depending on the type of radical initiator.

If there is too much oxygen during kneading,
It is desirable to knead the mixture substantially in the absence of oxygen since a gel-like substance may be formed or marked coloring may occur.

On the other hand, if the kneading temperature is lower than 200 ° C., the desired amount of unsaturated dicarboxylic anhydride to be added cannot be obtained, and only a small effect can be obtained for improving the graft reaction amount. Also 280
Even if the temperature exceeds ℃, the effect on the improvement of the amount of graft reaction is small, and in some cases, a gel-like substance is formed or coloring occurs, which is not preferable.

The kneading machine is not particularly limited for the purpose of denaturation, but it is generally preferable to use an extruder because continuous production is possible, and uniformly mix various raw materials supplied by one or two shafts. It is desirable to have a screw suitable for

An extruder is used to remove unreacted components (unsaturated carboxylic acid or derivative thereof, unsaturated aromatic monomer, radical initiator, etc.), oligomers, decomposition products, and other by-products from the reaction product. In the middle of or near the outlet, a method such as suctioning with a vacuum pump through a vent line, or dissolving the reaction product in an appropriate solvent, followed by precipitation and purification may be used. Further, it is also possible to carry out a heat treatment at a temperature of 60 ° C. or more and to evacuate under melting.

When the above three or four components are supplied to the kneader, they can be supplied separately, respectively.
Some or all of the components can be used as a uniform mixture. For example, a method in which an unsaturated aromatic monomer is impregnated into a rubber together with a radical initiator, and an unsaturated carboxylic acid or a derivative thereof is simultaneously fed during kneading to knead the rubber may be employed. Further, a method in which a radical initiator and / or an unsaturated carboxylic acid or a derivative thereof is supplied for modification from the middle of the extruder to perform modification may be used.

For the modified rubber-like substance (V), if necessary, an antioxidant, a heat stabilizer, a light stabilizer, a nucleating agent, a lubricant, an antistatic agent, an inorganic or organic coloring agent, a rust inhibitor, a crosslinking agent Various additives such as an agent, a foaming agent, a lubricant, a plasticity, a fluorescent agent, a surface smoothing agent, and a surface gloss improving agent can be added in a manufacturing process or a subsequent processing process.

The unsaturated carboxylic acid or its derivative and the radical initiator used in the modified rubber-like substance (V) include:
The compound can be selected from the compounds used in the production of the graft polypropylene (A). Styrene is most preferred as the unsaturated aromatic monomer, but o-methylstyrene, p-methylstyrene, α-methylstyrene, vinyltoluene and divinylbenzene can also be used. It is also possible.

In the method for producing the modified rubber-like substance (V), the unsaturated aromatic monomer is used for the purpose of preventing gel formation and improving the graft reaction amount. The amount of unsaturated aromatic monomer used is preferably 0.2 to 20 parts by weight based on 100 parts by weight of the raw rubber, and the amount of unsaturated carboxylic acid or its derivative is preferably used based on 100 parts by weight of the raw rubber. Is 0.5-1
5 parts by weight. When an aromatic monomer is used, the amount of the unsaturated carboxylic acid or derivative thereof is preferably 0.
It is preferably 5 to 15 parts by weight, and the weight ratio of unsaturated aromatic monomer / unsaturated carboxylic acid or its derivative is 0.1 to 3.0. The weight ratio of the unsaturated aromatic monomer is more preferably 0.5 to 2.0.

If the amount of unsaturated aromatic monomer used is less than 0.1% by weight based on the amount of unsaturated carboxylic acid or its derivative, there is no effect on prevention of gel formation and improvement of the amount of graft reaction, and 3.0% by weight. Even more than that, no more desirable effect can be expected.

The amount of the radical initiator used depends on the type of the radical initiator and the kneading conditions, but is usually based on 100 parts by weight of the raw rubber.
It can be used in the range of 0.005 to 1.0 part by weight, preferably 0.01 to 0.5 part by weight. If the amount is less than 0.005 parts by weight, the desired addition amount of the unsaturated carboxylic acid or its derivative cannot be obtained, and the effect of increasing the addition amount of the unsaturated carboxylic acid or its derivative by the combined use of the unsaturated aromatic monomer becomes small. On the other hand, if it is used in excess of 1.0 part by weight, the formation of a gel-like substance is undesirably excessive.

The modified rubber-like substance (V) thus obtained contains 0.1 to 5% by weight of an unsaturated carboxylic acid or a derivative thereof.
And the addition amount of the unsaturated aromatic monomer is preferably 0.1%.
And Mooney viscosity (ML _{1 + 4} 121 ° C) is 5 to 5% by weight.
Preferably it is 120.

As another method used in the production of the modified rubber-like substance (V), there is a method of copolymerizing in the main chain in the presence of a polymerization initiator and a catalyst. Generally, it can be produced by a known high-pressure radical polymerization method described below. It is obtained by copolymerizing ethylene with a monomer (comonomer) capable of undergoing radical copolymerization using a free radical generator such as organic peroxide or oxygen. The copolymerization reaction is usually 130
The reaction is carried out at a polymerization temperature of from 300 to 300 ° C. and under a polymerization pressure of from 500 to 3000 kg / cm ² .

The monomers capable of radical copolymerization include acrylic acid,
Examples include unsaturated carboxylic acids such as methacrylic acid and the like and esterified products thereof, and vinyl esters such as vinyl acetate. Specific examples of the esterified product of the unsaturated carboxylic acid include methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate and the like. These comonomers are not only one kind but also two.
More than one species can be used.

The content of the comonomer contained in the directly copolymerized modified rubber-like substance (V) is from 0.1 to 40% by weight, preferably from 1 to 35% by weight. If the comonomer content is less than 0.1% by weight, the modifying effect cannot be obtained.

Among these copolymers, those exemplified as ethylene copolymer rubber as a rubber-like substance as a raw material of the rubber-like substance (IV) and the modified rubber-like substance (V) are excluded.

Of these, ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer are preferred.

Inorganic filler, glass fiber (III) As the inorganic filler used in the present invention, talc (magnesium silicate), clay (aluminum silicate),
Zinc oxide, titanium oxide, calcium carbonate and the like can be mentioned. The average particle size of the preferred inorganic filler is 5.0 μm or less, more preferably, the average particle size is 5.0 μm or less, and the aspect ratio is 5 or more. A preferred inorganic filler is talc. The inorganic filler may be used without any treatment, but various silane coupling agents, titanium, etc. are used for the purpose of improving the interfacial adhesion with polyamide resin, polyphenylene ether resin, saturated polyester resin, etc. and improving dispersibility. Those whose surfaces have been treated with a coupling agent, higher fatty acid, higher fatty acid ester, higher fatty acid amide, higher fatty acid salt or another surfactant can be used.

The glass fiber used in the present invention is used in combination with an inorganic filler or used alone. Glass fiber can be used in combination with various coupling agents in order to improve interfacial adhesive and dispersibility with polyamide resin, polyphenylene ether resin, saturated polyester resin and the like. The coupling agent usually includes a silane-based or titanium-based coupling agent.

Composition ratio The thermoplastic resin composition according to the present invention comprises 100 parts by weight of a resin composition (I) comprising a polypropylene resin (A) and a thermoplastic resin (B) selected from a saturated polyester resin such as a polyamide resin and a polyphenylene ether resin. In contrast, as a compatibilizer, an unsaturated dicarboxylic acid compound having a carboxyl group in the molecule, or a derivative thereof,
It comprises 0 to 30 parts by weight of at least one compatibilizer selected from amine compounds having two or more nitrogen atoms in the molecule, or derivatives thereof, and epoxy group-containing copolymers.

100 parts by weight of the resin composition (I) contains 5 to 99.5% by weight, preferably 10 to 95% by weight, and more preferably 20 to 80% by weight of the polypropylene resin (A) as the first component. If the polypropylene resin (A) is less than 5% by weight, moldability, toughness, water resistance and chemical resistance are not sufficient, and if it exceeds 99.5% by weight, favorable properties in heat resistance, strength, rigidity, etc. Cannot be obtained.

When a modified polypropylene / polypropylene composition is used as the first component, the composition preferably contains 5% by weight or more of the modified polypropylene. If the amount is less than 5%, there is a problem in the compatibility and dispersibility of the final resin composition, so that sufficient toughness and impact resistance cannot be obtained, and improvement in paintability, adhesiveness, printability and the like is not sufficient.

At least one kind of thermoplastic resin (B) selected from saturated polyester resins such as polyamide resin and polyphenylene ether resin as the second component in the resin composition is 95 to 95%.
0.5% by weight, preferably 90-5% by weight, more preferably 8%
0-20% by weight is contained. 0.5% by weight of thermoplastic resin (B)
If it is less than 95%, the paintability, heat resistance, rigidity and strength are not sufficient, and if it exceeds 95% by weight, favorable properties in moldability, toughness, water resistance, chemical resistance, etc. cannot be obtained.

In the present invention, at least one selected from unsaturated carboxylic acid compounds having a carboxyl group in the molecule, or derivatives thereof, amine compounds having two or more nitrogen atoms in the molecule, or derivatives thereof, and epoxy group-containing copolymers The compatibilizer (II) is a polypropylene resin (A)
0 to 30 parts by weight based on 100 parts by weight of the total of at least one kind of thermoplastic resin (B) selected from saturated polyester resins such as polyamide resin and polyphenylene ether resin. If the amount exceeds 30 parts by weight, delamination occurs in the molded product, and the rigidity, toughness, impact resistance, etc. are significantly reduced, so that favorable results cannot be obtained.

In the thermoplastic resin composition of the present invention, a rubber-like substance (I) used for the purpose of improving impact resistance, particularly low-temperature impact resistance, is used.
V) or the modified rubber-like substance (V) is a resin composition (I) comprising a polypropylene resin (A) and at least one kind of thermoplastic resin (B) selected from saturated polyester resins such as polyamide resins and polyphenylene ether resins. Ten
0 to 100 parts by weight, preferably 1 to 70 parts by weight, per 0 parts by weight. If it exceeds 100 parts by weight, the toughness, heat resistance, etc. decrease, which is not preferable.

In the present invention, the amount of the inorganic filler and / or glass fiber (III) is 0 to 50 parts by weight based on 100 parts by weight of the resin composition (I). When no inorganic filler and / or glass fiber (III) is contained, the heat resistance, rigidity and dimensional stability are poor, but the impact strength is improved. If the content of the inorganic filler and / or glass fiber exceeds 50 parts by weight, the impact resistance is remarkably reduced, which is not preferable. A more preferred range is from 0 to 30 parts by weight. When the inorganic filler and the glass fiber are used together, the ratio of the inorganic filler to the glass fiber is 20 to 20 or more.
80% by weight.

Further, a pigment, an ultraviolet absorber, a heat stabilizer, a flame retardant, an antioxidant, a plasticizer, and the like can be added to the thermoplastic resin composition according to the present invention, if necessary.

Mixing method, molding method The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and a usual known method can be used.

Mixing in a solution state and evaporating the solvent or precipitating in a non-solvent is also effective, but from an industrial point of view, a method of kneading in a molten state is actually used. For the melt-kneading, a kneading device generally used such as a Banbury mixer, an extruder, a roll, various kneaders and the like can be used.

When kneading, it is preferable to uniformly mix each resin component in the form of powder or pellets in advance using a device such as a tumbler or Hensiel mixer. However, if necessary, the mixing is omitted and each resin component is separately set in a kneading device. Can also be used.

The kneaded resin composition is molded by injection molding, extrusion molding, or other various molding methods. However, the present invention does not pass through a kneading process in advance, but is dry-blended at the time of injection molding or extrusion molding and is subjected to a melt processing operation. To obtain a molded product by directly kneading the mixture.

In the present invention, the kneading order is not particularly limited, and the polypropylene resin (A), at least one kind of thermoplastic resin (B) selected from saturated polyester resins such as polyamide resin and polyphenylene ether resin, and unsaturated carboxylic acid compound Or at least one compatibilizing agent (II) selected from the group consisting of: or a derivative thereof, an amine compound or a derivative thereof, and an epoxy group-containing copolymer;
Alternatively, a method in which glass fiber (III), rubber-like substance (IV) and / or modified rubber-like substance (V) are added all at once, and melt-kneading is carried out simultaneously. Components (A) and (II) are added in the presence of a radical initiator. Alternatively, melt kneading is performed in the absence of the components, and then components (B), (III), (IV) and / or (V) are added and melt kneaded, and components (A), (II) and (IV) )
And / or (V) is previously melt-kneaded in the presence or absence of a radical initiator, and then the components (B) and (III)
Of the components (A) and (I) separately or separately by melt-kneading the components (B) and (III).
A method of melt-kneading I), (III), (IV) and / or (V) in the presence or absence of a radical initiator in advance, and then adding (B) additionally and melt-kneading the component (A) ),
(II), (IV) and / or (V) are previously melt-kneaded in the presence or absence of a radical initiator;
May be additionally kneaded, and the component (III) may be further added and melt-kneaded.

 Next, the surface treatment method and the coating method will be described.

In the present invention, the surface of the thermoplastic resin composition molded article is irradiated with ultraviolet rays.

In this case, the molded article of the thermoplastic resin composition can be a molded article of various shapes such as a film, a plate, and a fiber.

The light applied to the surface is light having a wavelength of 30 nm or less, particularly 254 nm.
UV light having a wavelength of 185 nm or 185 nm as a main working wavelength, and preferably has a higher intensity.

 The ultraviolet irradiation lamp is preferably made of synthetic quartz.

In the present invention, it is preferable to perform generally well-known degreasing before irradiating the surface of the molded article of the thermoplastic resin composition with ultraviolet rays.

Examples of the solvent for degreasing the surface of the molded article of the thermoplastic resin composition include water or an aqueous solution such as an alkali, and alcohols such as ethanol and isopropyl alcohol.

Methods for causing the solvent to reproduce on the surface of the molded article of the thermoplastic resin composition include methods such as coating or wiping, dipping, and spraying.

The ultraviolet irradiation time in the present invention is 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes. The effect of improving the paintability, adhesiveness, printability, etc. of the resin composition molded product shorter than 20 seconds is not sufficient, and longer than 10 minutes is not only economically disadvantageous, but also deteriorates the surface of the resin composition molded product. Occurs and has the opposite effect.

According to the present invention, after irradiating such ultraviolet rays, it is possible to apply an acrylic or urethane paint.

Preferred paints for use in the present invention include epoxy, polyester, acrylic and urethane paints.

In particular, urethane-based paints have flexibility and are widely used for automobile and motorcycle parts.

Examples of urethane-based paints include acrylic urethane, polyester urethane, and other paints having a urethane structure such as modified urethane.

<Examples> Hereinafter, the present invention will be described with reference to examples, but these are merely examples, and the present invention is not limited thereto.

(1) Raw materials used in Examples and Comparative Examples The modified polypropylene and the epoxy group-containing copolymer used in Examples and Comparative Examples were obtained by the following formulations. Commercially available polypropylene and polyamide resins were used.

Modified polypropylene It was produced with reference to the method described in JP-B-56-9925.

Polypropylene, maleic anhydride and tertiary butyl peroxylaurate were premixed. The extruder with a screw diameter of 30 mmφ, L / D28 is set at a barrel temperature of 230 ° C, the above mixture is supplied from a hopper, the extruder is reacted at a screw rotation speed of 60 rpm, and the modified polypropylene discharged from the die of the extruder. The molten strand was pelletized after water cooling.

 Polypropylene (i) Propylene homopolymer Sumitomo Noblene manufactured by Sumitomo Chemical Co., Ltd.  FS1012 (Melt flow rate: 1 g / 10 min) (ii) Propylene homopolymer Sumitomo Noblene manufactured by Sumitomo Chemical Co., Ltd.  W501 (melt flow rate: 8 g / 10 min) (iii) Propylene homopolymer Sumitomo Noblene manufactured by Sumitomo Chemical Co., Ltd.  WF299B (melt flow rate: 1.6g / 10min) Melt flow rate is measured according to JIS K6758.

Polyamide resin Polyamide 6 The relative viscosity by the JISK6810 98% sulfuric acid method and the amount of the functional group at the terminal of the polyamide resin by the neutralization titration method were as follows.

(I) PA-1; relative viscosity 2.3, amino group 71 mmol / kg, carboxyl group 71 mmol / kg (manufactured by Unitika Ltd., nylon A1025, hereinafter referred to as PA-1
(Ii) PA-2; relative viscosity 2.1, amino group 84 mmol / kg, carboxyl group 84 mmol / kg (Nylon A-1020BRL, manufactured by Unitika Ltd.)
(Iii) PA-3; PA-3; relative viscosity 2.35, amino group 94 mmol / kg, carboxyl group 54 mmol / kg (Nylon A-1030A, manufactured by Unitika Ltd., hereinafter referred to as PA
-3) Polyphenylene ether (hereinafter referred to as PPE) Obtained by dissolving 2,6-dimethylphenol in toluene and methanol, adding manganese chloride-ethylenediamine, and carrying out oxidative polymerization at a reaction temperature of 30 ° C in an oxygen atmosphere. Was.

 Saturated polyester resin polybutylene terephthalate; manufactured by Mitsubishi Rayon Co., Ltd.
 Tough pet PBT N1000 compatibilizer Maleic anhydride, 1.12-diaminododecane is commercially available.
Was used.

Epoxy group-containing copolymer Glycidyl methacrylate-ethylene-vinyl acetate copolymer The copolymer was produced with reference to the methods described in JP-A-47-23490 and JP-A-48-11388.

Use a 40-liter temperature-controllable stainless steel reactor equipped with appropriate supply and discharge ports and a stirrer to continuously supply glycidyl methacrylate, ethylene, vinyl acetate, radical initiator and chain transfer agent. The copolymerization was carried out under stirring at 1,400 to 1,600 atm and 180 to 200 ° C.

 Modified rubber-like substance Modified ethylene-propylene copolymer A modified rubber-like substance (V) was produced by the following method. number
Ethylene having an average molecular weight of 60,000 and an ethylene content of 78% by weight
Per 100 parts by weight of propylene copolymer rubber pellets
And 2.0 parts by weight of maleic anhydride and a radical initiator
As 1,3-bis (t-butylperoxyisopropyl
B) Benzene (manufactured by Sanken Kako Co., Ltd .: Samperox) −
8% by weight of TY1.3) supported on propylene homopolymer
Mixed with a Henschel mixer at a ratio of 1.0 part by weight.
And then the Japan Steel Works, Ltd. TEX44SS-30BW-2V
Using a twin screw extruder, under a nitrogen atmosphere, kneading temperature 250 ° C, extrusion
Melt kneading at an amount of 18 kg / hour, maleic anhydride addition amount 0.7
Weight%, Mooney viscosity at 121 ℃ (ML_{1 + 4}121 ° C) 72 denaturation
An ethylene-propylene copolymer rubber was produced.

 Inorganic filler Ultra fine talc micro manufactured by Nippon Talc Co., Ltd.
Ace P132 was used. Micro ace 50% average of P132
The particle diameter D50 is 2.1 μ as measured by the following measurement method.

Measuring instrument: Centrifugal sedimentation type particle size distribution analyzer, Shimadzu Corporation, Model SA-CP2-20 Rotation speed: 500 rpm Liquid level: 3 D50 was determined by plotting under sieve method.

(2) Paintability evaluation method (initial coating adhesion) Paint the surface of the molded product for measurement,
Carve 100 mm (10 vertical × 10 horizontal) of 2 mm goban eyes with a sled blade,
On top of that, 24mm width cellophane tape (Nichiban Co., Ltd.)
After pressing with your finger, grab the end face and pull off at once.
At the time of evaluation, the remaining number of stitches was evaluated as the remaining rate (%).
Valued.

Example 1 First, a method for producing a modified polypropylene will be described below.

 Homopolymer as base resin (Sumitomo Chemical Industries
Ltd., Sumitomo Noblen FS1012)
Modified with maleic acid to make maleic anhydride 0.11% by weight
To obtain modified polypropylene.

PA- as the above modified polypropylene and polyamide 6
1, and glycidyl methacrylate-ethylene-vinyl acetate copolymer (weight ratio: 10-85-5) were blended in the proportions shown in Table 1 and preliminarily mixed with a tumbler for 20 minutes, and then TEX44SS manufactured by Nippon Steel Corporation. Using a -30BW-2V type twin screw extruder,
Pellets were formed by melt-kneading at a temperature of 260 ° C. to obtain a resin composition. After drying this composition at 140 ° C. for 5 hours, a plate-like molded product is formed at a molding temperature of 280 ° C. and a mold temperature of 80 ° C. using a 10-oz injection molding machine (Toshiba Machine Co., Ltd., IS150E-V type). It was created.

The obtained molded product is used as a low-pressure mercury lamp (200 W made of synthetic quartz)
In the air atmosphere, the distance between the light source and the surface of the molded article is maintained at about 15 cm, and in the air atmosphere, ultraviolet rays having wavelengths of 254 nm and 185 nm as main working wavelengths (U
V) was irradiated for 60 seconds to perform surface treatment.

 Next, an acrylic urethane manufactured by Origin Electric Co., Ltd.
Tan paint origin plate Spray paint Z-NY, 8
Baking and drying at 0 ℃ for 30 minutes, initial adhesion of painted products
The degree was measured. Table 2 shows the results.

Example 2 Initial adhesion of a coated article was performed in the same manner as in Example 1 except that the paint was spray-coated using an acrylic urethane-based paint R271 manufactured by Nippon Bee Chemical Co., Ltd., and baked and dried at 90 ° C. for 30 minutes. Was measured. The results are shown in Table 2.

Example 3 Before irradiating with ultraviolet rays and performing surface treatment, the surface of the test piece was degreased with isopropyl alcohol (IPA), and the acrylic urethane paint R271 manufactured by Nippon Bee Chemical Co., Ltd. shown in Example 2 was used as the paint. In the same manner as in Example 1,
The initial adhesion of the coated product was measured. The results are shown in Table 2.

Comparative Example 1 The initial adhesion of the coated article was measured in the same manner as in Example 1 except that no ultraviolet irradiation was performed. The results are shown in Table 2.

Comparative Example 2 The initial adhesion of the coated article was measured in the same manner as in Example 1 except that the test piece was immersed in tetrachloroethylene at 60 ° C. for 60 seconds before irradiation with ultraviolet rays. The results are shown in Table 2.

Comparative Example 3 The initial adhesion of the coated product was measured in the same manner as in Example 2 except that no ultraviolet irradiation was performed. The results are shown in Table 2.

Comparative Example 4 The initial adhesion of the coated product was measured in the same manner as in Example 3 except that no ultraviolet irradiation was performed. The results are shown in Table 2.

Comparative Example 5 The initial adhesion of the coated article was measured in the same manner as in Example 2 except that the coating was immersed in tetrachloroethylene at 60 ° C. for 60 seconds before irradiation with ultraviolet rays. The results are shown in Table 2.

Example 4 Irradiation with ultraviolet light and isopropyl before surface treatment
Degreasing the surface of the test piece with alcohol
Modified urethane paint Flexen made by Chemical Co. # 101
The initial density of the coated product was the same as in Example 1 except that
The degree of attachment was measured. The results are shown in Table 2.

Comparative Example 6 The initial adhesion of the coated article was measured in the same manner as in Example 4 except that no ultraviolet irradiation was performed. The results are shown in Table 2.

Comparative Example 7 Unmodified polypropylene instead of modified polypropylene
(Sumitomo Noblen W501) (composition 3
(Shown in the table) measures the initial adhesion of the coated product in the same manner as in Example 1.
Specified. The results are shown in Table 4.

Example 5 Modified polypropylene, polyamide 6 and the like described in Example 1
And glycidyl methacrylate-ethylene-vinyl acetate
Copolymer and modified ethylene-propylene copolymer described above
After blending the coalesced with the blending described in Table 5, the same as in Example 1
A test piece is prepared on the surface, irradiated with ultraviolet light, and
Acrylic urethane paint Origipre made by Jin Electric Co., Ltd.
To Paint in Z-NY, bake and dry, paint
The initial adhesion of the product was measured. The results are shown in Table 6.

Comparative Example 8 The initial adhesion of the coated product was measured in the same manner as in Example 5 except that no ultraviolet irradiation was performed. The results are shown in Table 6.

Example 6 The modified polypropylene, polyamide 6 and glycidyl methacrylate-ethylene-vinyl acetate copolymer described in Example 1 and the modified ethylene-propylene copolymer described above were blended according to the formulation shown in Table 7, and then mixed with Example 1. With the same operation, the initial adhesion of the coated product was measured. Result 8
It is shown in the table.

Comparative Example 9 The initial adhesion of the coated article was measured in the same manner as in Example 6, except that no ultraviolet irradiation was performed. The results are shown in Table 8.

Example 7 After the modified polypropylene, polyamide 6 and glycidyl methacrylate-ethylene-vinyl acetate copolymer described in Example 2 and the modified ethylene-propylene copolymer described above were blended in the proportions shown in Table 9, the irradiation time was reduced. 12
The initial adhesion of the coated article was measured in the same manner as in Example 2 except that the time was set to 0 second. The results are shown in Table 10.

Example 8 First, a method for producing a co-modified polyolefin resin (A) / rubber-like substance will be described.

 Commercially available polypropylene homopolymer (Sumitomo Chemical Industries
Ltd., Sumitomo Noblen WF299B) and commercially available ethyl
Len-propylene copolymer rubber (manufactured by Sumitomo Chemical Co., Ltd.)
100 parts by weight of a mixture obtained by mixing E512P) at a ratio of 24.2 / 12.3
0.5 parts by weight of maleic anhydride, as a radical initiator
With 1,3-bis (t-butylperoxyisopropyl)
Nzen (Sanken Kako Co., Ltd .; Samperox) −TY1 ・
3) was carried on a propylene homopolymer at 8% by weight.
1.0 part by weight and Irganox as stabilizer 101
0 (manufactured by Ciba Geigy) 0.1 parts by weight of Henschel mixer
After mixing evenly with Nippon Steel Corporation, TEX44SS-30BW
Temperature of 220 ° C, average residence time 1.5 minutes with a −2V type twin screw extruder
Melt kneading with a melt flow rate of 14 (g / 10 minutes)
A propylene / rubber co-modified resin composition was produced. Below
This is abbreviated as M- (PP / EPM) -1.

M- (PP / EPM) -1 and PA-2 as polyamide, and
PA-3, glycidyl methacrylate-ethylene-vinyl acetate copolymer and talc (provided that PA-2 and talc are
A resin composition molded article was prepared in the same manner as in Example 1 except that the mixture was melt-kneaded at 230 ° C. in advance using a twin-screw kneader at a ratio shown in Table 11, and then irradiated with ultraviolet rays. Surface treatment.

 Next, an acrylic urethane system manufactured by Fujikura Kasei Co., Ltd.
Paint lek rack Spray paint # 440H and bake at 80 ℃ for 30 minutes
After drying by rubbing, measure the initial adhesion of the painted product.
Was. Table 12 shows the results.

Example 9 The initial adhesion of the coated product was measured in the same manner as in Example 8, except that the surface of the test piece was degreased with isopropyl alcohol (IPA) before the surface treatment was performed by irradiating with ultraviolet rays. Table 12 shows the results.

Comparative Example 10 The initial adhesion of the coated article was measured in the same manner as in Example 8 except that no ultraviolet irradiation was performed. Table 12 shows the results.

Comparative Example 11 The initial adhesion of the coated article was measured in the same manner as in Example 9 except that no ultraviolet irradiation was performed. Table 12 shows the results.

Example 10 Polyphenylene ether manufactured by Nippon Polyether Co., Ltd.
Resin (Reduction measured at 25 ° C in chloroform 0.5g / dl concentration)
Viscosity 0.46g / dl), polypropylene homopolymer (Sumitomo Chemical)
Manufactured by Gaku Kogyo Co., Ltd., Sumitomo Noblen WF299B)
Compound as maleic anhydride, styrene, radical initiator
With 1,3-bis (t-butylperoxyisopropyl)
Nzen (Sanken Kako Co., Ltd .; Samperox) −TY1 ・
3), Table 13 shows 1.12-diaminododecane as a compatibilizer.
Mix in the proportions described and premix with a tumbler.
Melt at 260 ° C using a kneading machine (TEM-50 manufactured by Toshiba Machine)
After kneading, a pellet-like fat composition was obtained.

The obtained resin composition was injected into an injection molding machine (IS-15 manufactured by Toshiba Machine Co., Ltd.).
Injection molding was performed at 0E) to produce a plate-like molded product.

The obtained molded product is used as a low-pressure mercury lamp (200 W made of synthetic quartz)
Is placed in front of an ultraviolet irradiation device equipped with a 254 nm light source, and the distance between the light source and the surface of the molded product is 10 cm.
Ultraviolet rays having a wavelength of 185 nm as a main working wavelength were irradiated for 60 seconds to perform surface treatment.

Next, the surface was spray-coated with an acrylic urethane-based paint R271 manufactured by Nippon Bee Chemical Co., Ltd., baked and dried at 90 ° C. for 30 minutes, and the initial adhesion of the coated molded product was measured. Table 14 shows the results.

Example 11 The initial adhesion of the coated article was measured in the same manner as in Example 10 except that the surface of the test piece was degreased with isopropyl alcohol (IPA) before the surface treatment was performed by irradiating with ultraviolet rays. Table 14 shows the results.

Comparative Example 12 The initial adhesion of the coated product was measured in the same manner as in Example 10, except that no ultraviolet irradiation was performed. Table 14 shows the results.

Comparative Example 13 The initial adhesion of the coated product was measured in the same manner as in Example 11, except that no ultraviolet irradiation was performed. Table 14 shows the results.

Example 12 First, a method for producing a co-modified polyolefin resin (A) / rubber-like substance will be described.

A polypropylene / rubber co-modified resin composition was prepared in the same manner as in M- (PP / EPM) -1 in Example 8 except that the ratio of the polypropylene homopolymer and the ethylene-propylene copolymer rubber was changed to 45/13. Was manufactured. Hereinafter, this is abbreviated as M- (PP / EPM) -2.

 As M- (PP / EPM) -2 and saturated polyester resin,
Polybutylene terephthalate (manufactured by Mitsubishi Rayon Co., Ltd.
Tough pet PBT N-1000), glycidyl methacrylate
The proportions of tri-ethylene-vinyl acetate copolymer described in Table 15
After pre-mixing with Henschel mixer,
Using a steel mill (manufactured) TEX-44SS-30BW-2V type twin screw extruder
And melt-knead at 250 ° C to obtain a pellet-shaped resin composition.
Was.

After pre-drying the obtained resin composition at 120 ° C. for 2 hours,
Using an IS-150E injection molding machine manufactured by Toshiba Machine Co., Ltd., a plate-like molded product was prepared at a molding temperature of 240 ° C. and a mold temperature of 70 ° C.

The obtained molded product is used as a low-pressure mercury lamp (200 W made of synthetic quartz)
Is placed in front of an ultraviolet irradiation device equipped with a 254 nm light source, and the distance between the light source and the surface of the molded product is 10 cm.
Ultraviolet light (UV) with 185 nm wavelength light as the main working wavelength
Was irradiated for 120 seconds to perform a surface treatment.

Next, an acrylic urethane paint R271 manufactured by Nippon Bee Chemical Co., Ltd. was spray-coated on the surface, baked and dried at 90 ° C. for 30 minutes, and the initial adhesion of the coated molded product was measured. Table 16 shows the results.

Comparative Example 14 The initial adhesion of the coated article was measured in the same manner as in Example 12, except that no ultraviolet irradiation was performed.

 Table 16 shows the results.

<Effects of the Invention> As described above, according to the present invention, a surface treatment method for a thermoplastic resin composition molded article having extremely excellent coatability, adhesiveness, printability, and the like, and a method for coating the molded article are provided. can do.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 77/00 C08L 77/00 (72) Inventor Satoru Sokabe 5-1 Anesaki Kaigan, Ichihara-shi, Chiba Sumitomo Chemical Industries, Ltd. (56) References JP-A-61-64741 (JP, A) JP-A-60-166332 (JP, A) JP-A-60-181161 (JP, A) JP-A-3-217432 (JP, A) Kaihei 1-263127 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08J ⁷ /00-7/18 C08L 1/00-101/14

Claims (29)

(57) [Claims] 1. Polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition in an amount of 5 to 99.5% by weight, a polyamide resin, a polyphenylene ether resin, a mixture of a polyphenylene ether resin and a styrene resin, and a polyphenylene ether resin. A polypropylene-based resin (A) is added to 100 parts by weight of a resin composition (I) consisting of 95 to 0.5% by weight of at least one thermoplastic resin (B) selected from a graft copolymer with styrene and a saturated polyester resin. As a compatibilizer for improving the compatibility between the compound and a thermoplastic resin (B), such as an unsaturated carboxylic acid compound having a carboxyl group in the molecule or a derivative thereof, an amine compound having two or more nitrogen atoms in the molecule, Or selected from its derivatives and epoxy group-containing copolymers Not even one of the compatibilizer (I
I) 3 to 3 parts by weight of the resin composition molded product
A surface treatment method for a resin composition molded article, which comprises irradiating an ultraviolet ray having an irradiation wavelength to a region of 00 nm or less. 2. The resin according to claim 1, wherein the resin composition (I) comprises 10 to 95% by weight of a polypropylene resin (A) and 90 to 5% by weight of a thermoplastic resin (B). A method for treating the surface of a molded composition. 3. Polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition in an amount of 5 to 99.5% by weight, a polyamide resin, a polyphenylene ether resin, a mixture of a polyphenylene ether resin and a styrene resin, and a polyphenylene ether resin. A polypropylene resin (A) is added to 100 parts by weight of a resin composition (I) comprising 95 to 0.5% by weight of at least one thermoplastic resin (B) selected from a graft copolymer with styrene and a saturated polyester resin. ) As a compatibilizer for improving the compatibility between the thermoplastic resin (B) and an unsaturated carboxylic acid compound having a carboxyl group in the molecule, or a derivative thereof, or an amine compound having two or more nitrogen atoms in the molecule Or a derivative thereof and an epoxy group-containing copolymer At least one compatibilizing agent (I
I) 3 to 3 parts by weight of the resin composition molded product
After irradiating the area below 00nm with ultraviolet light having the irradiation wavelength,
A method for painting a resin composition molded article, characterized by painting with a paint. 4. The resin according to claim 3, wherein the resin composition (I) comprises 10 to 95% by weight of the polypropylene resin (A) and 90 to 5% by weight of the thermoplastic resin (B). A method for coating a composition molded article. 5. A polyamide resin (B) containing 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition.
100 to 100 parts by weight of a resin composition (I) comprising 95 to 0.5% by weight;
A region of 300 nm or less is irradiated onto the surface of a molded product obtained by molding a resin composition comprising 0 to 30 parts by weight of an epoxy group-containing copolymer and 0 to 50 parts by weight of an inorganic filler and / or glass fiber (III). A surface treatment method for a resin composition molded article, which comprises irradiating an ultraviolet ray having a wavelength for 20 seconds to 10 minutes. 6. A polyamide resin (B) containing 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition.
100 to 100 parts by weight of a resin composition (I) comprising 95 to 0.5% by weight;
A region of 300 nm or less is irradiated onto the surface of a molded product obtained by molding a resin composition comprising 0 to 30 parts by weight of an epoxy group-containing copolymer and 0 to 50 parts by weight of an inorganic filler and / or glass fiber (III). A method for coating a resin composition molded article, comprising irradiating with ultraviolet light having a wavelength for 20 seconds to 10 minutes and then coating with a paint. 7. A polyamide resin (B) containing 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition.
100 to 100 parts by weight of a resin composition (I) comprising 95 to 0.5% by weight;
0.1-30 parts by weight of epoxy group-containing copolymer, rubber-like substance (I
V) and / or modified rubber-like substance (V) 0.1 to 100 parts by weight, and inorganic filler and / or glass fiber (III)
A molded article obtained by molding a resin composition consisting of 0 to 50 parts by weight is irradiated with an ultraviolet ray having an irradiation wavelength in a region of 300 nm or less for 20 seconds to 10 seconds.
A method for surface treatment of a resin composition molded article, which comprises irradiating the molded article with a resin composition. 8. A polyamide resin (B) containing 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition.
100 to 100 parts by weight of a resin composition (I) comprising 95 to 0.5% by weight;
0.1-30 parts by weight of epoxy group-containing copolymer, rubber-like substance (I
V) and / or modified rubber-like substance (V) 0.1 to 100 parts by weight, and inorganic filler and / or glass fiber (III)
UV light having an irradiation wavelength in a region of 300 nm or less is applied to a molded product obtained by molding a resin composition consisting of 0 to 50 parts by weight for 20 seconds to 10 seconds.
A method for coating a resin composition molded article, comprising irradiating with a paint after irradiation for one minute. 9. A polyamide resin (B) containing 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition.
Molding by molding a resin composition comprising 95 to 0.5% by weight of a resin composition (I) of 100 parts by weight and a rubber-like substance (IV) and / or a modified rubber-like substance (V) of 0.1 to 100 parts by weight. UV light with an irradiation wavelength in the region of 300 nm or less
A method for surface treatment of a molded article of a resin composition, which comprises irradiating for 20 seconds to 10 minutes. 10. The resin composition according to claim 1, wherein the resin composition (I) comprises 10 to 95% by weight of a polypropylene resin (A) and 90 to 5% by weight of a polyamide resin (B). 9
A surface treatment method for the resin composition molded article according to the above. 11. A resin composition (I) consisting of 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition and 95 to 0.5% by weight of a polyamide resin (B), and 100% by weight. Parts, rubber-like substance (IV) and / or modified rubber-like substance (V) 0.1 to 100 parts by weight, and inorganic filler and / or glass fiber (III) 0 to 50 parts by weight to form a resin composition. A method for coating a resin composition molded article, comprising irradiating a molded article with ultraviolet rays having an irradiation wavelength in a region of 300 nm or less for 20 seconds to 10 minutes, and then applying a paint. 12. The resin composition according to claim 3, wherein the resin composition (I) comprises 10 to 95% by weight of a polypropylene resin (A) and 90 to 5% by weight of a polyamide resin (B). 11
A method for coating a resin composition molded article according to the above. 13. 100% by weight of a resin composition (I) comprising 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition and 95 to 0.5% by weight of a polyphenylene ether resin (B). Parts by weight, 0 to 100 parts by weight of rubber-like substance (IV) and / or modified rubber-like substance (V), 0 to 50 parts by weight of inorganic filler and / or glass fiber (III), and Molding of a resin composition comprising an unsaturated carboxylic acid compound having a carboxyl group in the molecule or a derivative thereof in an amount of 0.01 to 10 parts by weight and / or an amine compound having two or more nitrogen atoms in the molecule or a derivative thereof in an amount of 0.01 to 10 parts by weight. A method for surface treating a resin composition molded article, comprising irradiating the article with ultraviolet light having an irradiation wavelength in a region of 300 nm or less for 20 seconds to 10 minutes. 14. A resin composition (I) comprising 10 to 95% by weight of a polypropylene resin and a polyphenylene ether resin (B).
14. The method for treating a surface of a resin composition molded product according to claim 13, wherein the content is 90 to 5% by weight. 15. The method for surface treatment of a molded article of a resin composition according to claim 13, wherein the unsaturated carboxylic acid compound having a carboxyl group in the molecule as the compatibilizer or the derivative thereof is maleic anhydride. 16. An amine compound having two or more nitrogen atoms in a molecule as a compatibilizer or its derivative is 1,12-
The surface treatment method for a resin composition molded article according to any one of claims 13 to 15, which is diaminododecane. 17. A polyphenylene ether resin (B) comprising:
The surface treatment method for a resin composition molded article according to any one of claims 13 to 16, wherein the resin composition is poly (2,6-dimethyl-1,4phenylene) ether. 18. 100% by weight of a resin composition (I) comprising 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition and 95 to 0.5% by weight of a polyphenylene ether resin (B) Parts by weight, 0 to 100 parts by weight of rubber-like substance (IV) and / or modified rubber-like substance (V), 0 to 50 parts by weight of inorganic filler and / or glass fiber (III), and Molded article of a resin composition comprising an unsaturated carboxylic acid compound having a carboxyl group in the molecule or its derivative 0.01 to 10 parts by weight and / or an amine compound having two or more nitrogen atoms in the molecule or its derivative 0.01 to 10 parts by weight A method for coating a resin composition molded article, comprising: irradiating an ultraviolet ray having an irradiation wavelength to a region of 300 nm or less for 20 seconds to 10 minutes, and then coating with a paint. 19. A resin composition (I) comprising 10 to 95% by weight of a polypropylene resin and a polyphenylene ether resin (B).
19. The method for coating a resin composition molded product according to claim 18, wherein the content is 90 to 5% by weight. 20. The method for coating a resin composition molded article according to claim 18, wherein the unsaturated carboxylic acid compound having a carboxyl group in the molecule as the compatibilizer or the derivative thereof is maleic anhydride. 21. An amine compound having two or more nitrogen atoms in a molecule as a compatibilizer, or a derivative thereof is 1,12-
The method for coating a resin composition molded article according to any one of claims 18 to 20, which is diaminododecane. 22. A polyphenylene ether resin (B) comprising:
The method for coating a resin composition molded article according to any one of claims 18 to 21, wherein the method is poly (2,6-dimethyl-1,4phenylene) ether. 23. The method according to claim 3, wherein the paint is a urethane paint.
The method for coating a resin composition molded article according to 6, 8, 11, 12, 18, 19, 20, 21, or 22. 24. 100% by weight of a resin composition (I) comprising 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition and 95 to 0.5% by weight of a saturated polyester resin (B). Parts, Epoxy group-containing copolymer (III) 0.1 to 30 parts by weight,
Rubber-like substance (IV) and / or modified rubber-like substance (V)
A molded article of a resin composition comprising 0 to 100 parts by weight and 0 to 50 parts by weight of an inorganic filler and / or glass fiber (III) is irradiated with ultraviolet rays having an irradiation wavelength in a region of 300 nm or less for 20 seconds to 10 minutes.
A method for surface treatment of a resin composition molded article, which comprises irradiating the molded article with a resin composition. 25. The method according to claim 24, wherein the resin composition (I) comprises 10 to 95% by weight of a polypropylene resin and 90 to 5% by weight of a saturated polyester resin (B). 26. An epoxy group-containing copolymer which is a copolymer comprising an unsaturated epoxy compound and ethylene, or a copolymer comprising an unsaturated epoxy compound, ethylene and an ethylenically unsaturated compound other than ethylene. 1,2,5,
27. The surface treatment method for a resin composition molded article according to 7, 24 or 25. 27. 100% by weight of a resin composition (I) comprising 5 to 99.5% by weight of a polypropylene resin (A) selected from a modified polypropylene and a modified polypropylene / polypropylene composition and 95 to 0.5% by weight of a saturated polyester resin (B). Parts, epoxy group-containing copolymer 0.1 to 30 parts by weight, rubber-like substance (IV) and / or modified rubber-like substance (V) 0 to 10
0 parts by weight, and an inorganic filler and / or glass fiber (I
II) 300 nm for molded articles of resin composition consisting of 0 to 50 parts by weight
A method for coating a resin composition molded article, comprising irradiating an ultraviolet ray having an irradiation wavelength to the following region for 20 seconds to 10 minutes, and then coating with a paint. 28. The method according to claim 27, wherein the resin composition (I) is 10 to 95% by weight of a polypropylene resin and 90 to 5% by weight of a saturated polyester resin (B). 29. The epoxy group-containing copolymer is a copolymer comprising an unsaturated epoxy compound and ethylene, or a copolymer comprising an unsaturated epoxy compound, ethylene and an ethylenically unsaturated compound other than ethylene. 3,4,6,
29. The method for coating a resin composition molded article according to 8, 27 or 28.