JP2003277570A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition with its surface scratch resistance improved without degradation in mechanical strength such as impact strength and surface appearance after molding, and high in weather resistance, and to provide a thermoplastic resin composition for laser marking producing moldings excellent in scratch resistance. <P>SOLUTION: The thermoplastic resin composition contains 0.1-50 pts.wt., relative to 100 pts.wt of a rubber-modified thermoplastic resin, of a lamellar clay mineral intercalating an organic compound, and produces the thermoplastic resin composition for laser marking. The lamellar clay mineral is e.g. a smectite- based clay, a montmorillonite-based clay, a mica mineral or the like. As for the organic compound to be intercalated by the lamellar clay mineral, it preferably has a structure with a ≥6C alkyl group and ionizable polar groups at its ends. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent physical properties such as impact resistance, molding appearance, scratch resistance, weather resistance and molding processability. Further, the present invention provides
TECHNICAL FIELD The present invention relates to a thermoplastic resin composition for laser marking, which exhibits clear and hard-to-remove marking by irradiating a resin surface of a molded article with laser light, and has excellent scratch resistance of the marking surface.

[0002]

2. Description of the Related Art Rubber-modified thermoplastic resins have excellent physical properties such as impact strength and are used in various fields. In particular, ethylene-α-, which has good weather resistance for rubber
A rubber-modified resin with good weather resistance, which uses hydrogenated rubber such as olefin rubber, acrylic ester rubber, hydrogenated butadiene rubber, and silicon rubber, has good weather resistance. It can be used without performing, and is useful for cost reduction and environmental conservation. However, when the usage time is long, surface scratches may become a problem, and there is a limit to scratch resistance depending on the application, and as a result, the feature of good weather resistance may not be fully utilized. is there.

In order to improve the scratch resistance, the amount of rubber is lowered to harden the surface, or the sliding property is imparted to provide surface lubricity, and when an object comes into contact, it is slid to prevent scratches, and inorganic Measures have been taken such as adding a filler to increase the surface hardness. Decreasing the amount of rubber increases hardness and has some effect, but rather reduces impact strength.
There is a limit to the range of measures that can be taken, and there is a limit to the balance between impact strength and scratch resistance.

The addition of the inorganic filler is effective in improving the surface hardness, and the scratch resistance of the surface is remarkably improved by the addition amount of several% to several tens%. However, the appearance of the filler on the surface significantly deteriorates the appearance, and the product value is almost lost, and there is a limit as a countermeasure. In particular, in the case of a weather resistant material, since the surface is not decorated, the method of adding a filler has a direct adverse effect on the molding appearance, and it cannot be used at all for a material having a good molding appearance.

When an additive or the like is added for imparting slidability, the glass transition temperature (Tg) becomes lower as the amount of the additive becomes larger, which causes a problem in heat resistance and lowers impact strength. Sometimes. Further, there is a method of adding a polymer having good slidability, such as polyoxymethylene or high-density polyethylene (HDPE), but it is often impractical because of compatibility problems.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to improve the scratch resistance of the surface without impairing the mechanical strength such as impact strength and the surface appearance after molding, and to provide a thermoplastic resin having excellent weather resistance. It is to provide a resin composition. Another object of the present invention is to provide a thermoplastic resin composition for laser marking, which is capable of obtaining a molded article having excellent scratch resistance, such as a molded article such as a keyboard printed by laser marking.

[0007]

According to the present invention, 0.1 to 50 parts by weight of a layered clay mineral in which an organic compound is intercalated is contained with respect to 100 parts by weight of a rubber-modified thermoplastic resin. A thermoplastic resin composition comprising: Further, there is provided a thermoplastic resin composition for laser marking, which comprises the above-mentioned thermoplastic resin composition of the present invention.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. [Rubber-Modified Thermoplastic Resin] The rubber-modified thermoplastic resin of the present invention (hereinafter, simply referred to as “rubber-modified resin”) is, for example, an aromatic vinyl compound, a vinyl cyanide compound, (meta) in the presence of a rubber polymer. ) It can be obtained by polymerizing a vinyl monomer such as an acrylate compound.

(Rubber-like polymer) As the rubber-like polymer,
Natural rubber, polybutadiene rubber, polyisoprene rubber,
Polychloroprene rubber, styrene-butadiene random copolymer rubber (styrene content is preferably 5 to 60% by weight), styrene-isoprene random copolymer rubber, acrylonitrile-butadiene random copolymer rubber, isobutylene-isoprene random copolymer rubber (butyl rubber) , Styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, styrene-isoprene-styrene block copolymer rubber, and other diene rubbers; hydrogenated rubbers of the above diene rubbers such as SEBS;
Ethylene-α-olefin copolymer rubber, ethylene-α
-Ethylene-α-olefin copolymer rubber such as olefin-non-conjugated diene compound copolymer rubber; acrylate ester rubber, acrylate ester-aromatic vinyl copolymer rubber, acrylate ester-conjugated diene compound copolymer rubber, acrylic Acrylic rubbers such as acid ester compounds-conjugated diene compounds-aromatic vinyl compound copolymer rubbers; and silicone rubbers.

Of these rubbers, it is preferable to use a rubber-like polymer having good weather resistance. Rubber with good weather resistance has high stability even when exposed to light, heat, moisture, oxygen, and other pollutants, and the rubber modified resin using this requires surface decoration such as painting and treatment. No, it can be used as it is after molding. Therefore, it not only contributes to the cost reduction required for the surface treatment, but also does not release the organic solvent due to the coating, and thus the load on the environment is small. Examples of the rubber having good weather resistance that is preferably used include rubbers having substantially no double bond in the main chain. Specifically, ethylene-α-olefin copolymer rubbers, ethylene-α-olefin-non-conjugated diene compound copolymer rubbers and other ethylene-α-olefin copolymer rubbers; acrylic ester-aromatic vinyl copolymer rubbers. , Acrylic acid ester-conjugated diene compound copolymer rubber, acrylic ester compound-conjugated diene compound-aromatic vinyl compound copolymer rubber, etc. Acrylic rubber with virtually no double bonds in the chain;
Hydrogenated rubbers of the above diene rubbers such as SEBS; silicone rubbers and the like. The above-mentioned "having substantially no double bond in the main chain" means having a double bond in the main chain only to such an extent that the weather resistance is not impaired even if it has a double bond. The upper limit of the allowable amount of double bonds varies depending on the type of rubber-like polymer and cannot be determined uniquely, but can be determined by conducting appropriate experiments for each type.

These rubber-like polymers may be used alone or in combination.
It is possible to blend and use one or more species. Further details regarding these preferred rubbery polymers are provided.

(A) Ethylene-α-olefin copolymer rubber As the ethylene-α-olefin copolymer rubber, for example, ethylene / α-olefin having 3 to 20 carbon atoms / non-conjugated diene = 5 to 95/95 to A copolymer rubber obtained by copolymerizing a monomer having a mixing ratio of 5/0 to 30% by weight can be mentioned. Examples of the α-olefin having 3 to 20 carbon atoms here include propylene, 1-butene, 1-pentene, 1-
Hexene, 4-methyl-1-pentene, 1-heptene,
1-octene, 1-decene, 1-dodecene and the like can be mentioned. Propylene, 1-butene and 1-octene are preferred, and propylene and 1-butene are more preferred. These α-olefins may be used alone or in combination of two or more. The carbon number of α-olefin is 3 to
20 but preferably 3 to 12, more preferably 3
~ 8. When the carbon number is too large, the copolymerizability is extremely lowered. Ratio of ethylene and α-olefin (ethylene /
α-olefin) is preferably 5 to 95/95 to 5,
It is more preferably 50 to 90/50 to 10, and particularly preferably 40 to 85/60 to 15.

The non-conjugated diene compounds which may be used in combination include alkenyl norbornenes, cyclic dienes,
Examples thereof include aliphatic dienes, and dicyclopentadiene and 5-ethylidene-2-norbornene are preferable. These non-conjugated dienes can be used alone or in combination of two or more. The content of the non-conjugated diene in the ethylene-α-olefin copolymer rubber is 0 to 30% by weight, preferably 0 to 15% by weight. The unsaturated amount of this copolymer rubber is preferably in the range of 0 to 40 in terms of iodine value. If the amount of unsaturation is too large, the weather resistance (light) resistance,
The hue becomes incompatible.

In order to obtain these ethylene-α-olefin copolymer rubbers, either a homogeneous catalyst or a heterogeneous catalyst may be used. Examples of the homogeneous catalyst include metallocene catalysts. As the heterogeneous catalyst, for example, a vanadium catalyst in which a vanadium compound and an organic aluminum compound are combined can be mentioned.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the ethylene-α-olefin copolymer rubber is preferably 60 or less, more preferably 50 or less, and particularly preferably 20 to 40. The glass transition temperature of the ethylene-α-olefin copolymer rubber is preferably -110.
-40 degreeC, More preferably, it is -70-45 degreeC.

(B) Acrylic rubber As an acrylic rubber, the alkyl group has 2 to 8 carbon atoms.
Is a polymer of alkyl acrylate or a copolymer thereof. Specific examples of the acrylate ester include ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate. These can be used alone or in combination of two or more. Preferred acrylic acid esters are n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate.

A part of the acrylic acid ester used for the acrylic rubber can be replaced with another copolymerizable monomer. Such other monomers include
Examples thereof include aromatic vinyl compounds, methacrylic acid ester compounds and conjugated diene compounds. Among them, aromatic vinyl compounds are preferable, and styrene is preferable among them. Further, when butadiene is used as the conjugated diene compound, it is desirable to use it in the range of 40% by weight or less of the total amount of rubber in consideration of weather resistance. However, when it is used in a larger amount, a layered structure is adopted to form a polybutadiene layer. Should be the core part.

The type and amount of the monomers of the acrylic rubber are preferably selected so that the glass transition temperature thereof is -10 ° C or lower. Moreover, it is preferable that the acrylic rubber is appropriately copolymerized with a crosslinkable monomer. The amount of the crosslinkable monomer used in the acrylic rubber is preferably 0 to 10% by weight, more preferably 0.01 to 10% by weight, still more preferably 0.1 to 5% by weight. Suitable crosslinkable monomers include mono- or polyethylene glycol diacrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene. Mono- or polyethylene glycol dimethacrylate such as glycol dimethacrylate and tetraethylene glycol dimethacrylate; polyvinyl aromatic compounds such as divinylbenzene; polyallyl compounds such as diallyl phthalate, diallyl maleate, diallyl succinate and triallyl triazine; allyl methacrylate Allyl (meth) acrylates such as -to, allyl acrylate;
Examples thereof include conjugated diene compounds such as 1,3-butadiene and isoprene. The acrylic rubber is produced by a known polymerization method, but an emulsion polymerization method or a suspension polymerization method is preferable.

(C) Silicone-based rubber The silicone-based rubber is preferably a polyorganosiloxane-based rubber-like polymer obtained in a latex state by emulsion polymerization because of the ease of graft polymerization. The latex of the polyorganosiloxane rubber-like polymer can be obtained by a known method, for example, the method described in US Pat. No. 3,294,725. A preferred method is to produce organosiloxane by shear-mixing with water using a homomixer or an ultrasonic mixer in the presence of a sulfonic acid-based emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid to cause condensation. it can.
At this time, alkylbenzene sulfonic acid and the like act as an emulsifying agent for the organosiloxane and at the same time serve as a polymerization initiator, and are therefore preferably used. Among them, the alkylbenzene sulfonic acid metal salt and the alkyl sulfonic acid metal salt are preferable because they are effective in maintaining the polymer stably during the graft polymerization. If necessary, the graft crossing agent and the cross-linking agent may be co-condensed within a range that does not impair the intended performance of the present invention.

The organosiloxane has, for example, a structural unit represented by the following general formula (1), and is an organosiloxane having a linear, branched or cyclic structure, preferably a cyclic structure. General formula (1): R _m SiO _{(4-m) / 2} (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and m represents an integer of 0 to 3) of this organosiloxane Examples of the substituted or unsubstituted monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a phenyl group, and a substituted hydrocarbon group obtained by substituting them with a cyano group or the like.

Specific examples of the organosiloxane include cyclic organosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane. Examples thereof include linear organosiloxanes and branched organosiloxanes. These organosiloxanes may be used alone or in combination of two or more. Further, the organosiloxane may be a polyorganosiloxane that has been condensed in advance and has a polystyrene-equivalent weight average molecular weight of about 500 to 10,000. When the organosiloxane is a polyorganosiloxane, its molecular terminal may be blocked with a hydroxyl group, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, a methyldiphenylsilyl group, or the like. The above-mentioned organosiloxanes may be used alone or in the form of 2
It is also possible to use a combination of two or more species.

Further, a graft crossing agent can be used within a range that does not impair the achievement of the object of the present invention. Examples of the graft crossing agent used include the following. ^{_{(B) CH 2 = C (R 1}} ) - (Ph) - ( wherein, ^{R 1} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ph represents a phenylene group) unsaturated represented by A crosslinker that has both groups and alkoxysilyl groups. (B) R ² _p SiO ² _{(3-p) / 2} (In the formula, R ² is a vinyl group or an allyl group, and p is an integer of 0 to 2.) Specific examples: vinylmethyldimethoxysilane, tetravinyltetramethyl Cyclosiloxane, allylmethyldimethoxysilane. (C) HSR ³ SiR ⁴ _q O _{(3-q) / 2} (wherein R
³ is a divalent or trivalent saturated aliphatic hydrocarbon group having 1 to 18 carbon atoms, R ⁴ is a monovalent hydrocarbon group containing no aliphatic unsaturated group having 1 to 6 carbon atoms, and q is 0. Indicates an integer of ˜2. ) Specific example: γ-mercaptopropylmethyldimethoxysilane. _{(D) CH 2 = C (CH 3} ) -COO- (CH 2) r S
iR ⁵ _s O _{(3-s) / 2} (wherein R ⁵ is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a phenyl group, r is an integer of 1 to 6, and s is 0 to 2).
Indicates an integer. ) Specific example: γ-methacryloxypropylmethyldimethoxysilane.

Of these graft crossing agents, a compound having an unsaturated group and an alkoxysilyl group represented by the above (a) is particularly preferable. Specific examples of the compound (a) include p-vinylphenylmethyldimethoxysilane, 1- (m-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 3-. (P-Vinylphenoxy) propylmethyldiethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane , 1- (p-vinylphenyl) -1,1-diphenyl-3-ethyl 3,3-
Diethoxydisiloxane, m-vinylphenyl- [3-
(Triethoxysilyl) propyl] diphenylsilane,
[3- (p-isopropenylbenzoylamino) propyl] phenyldipropoxysilane, 2- (m-vinylphenyl) ethylmethyldimethoxysilane, 2- (o-vinylphenyl) ethylmethyldimethoxysilane, 1-
In addition to (p-vinylphenyl) ethylmethyldimethoxysilane, 1- (o-vinylphenyl) ethylmethyldimethoxysilane and the like, a mixture thereof can be mentioned. Of these graft crossing agents, preferably p-
Vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 3-
(P-Vinylbenzoyloxy) propylmethyldimethoxysilane, and more preferably p-vinylphenylmethyldimethoxysilane.

When the graft crossing agent is used, the amount thereof is preferably 0.1 to 30% by weight, more preferably 0.2 to 2 in the total amount of the organosiloxane and the crossing agent.
It is 0% by weight, particularly preferably 0.5 to 5% by weight. When the amount of the graft crossing agent is large, the molecular weight of the grafted polymer is lowered and sufficient impact resistance cannot be obtained. 0.1% by weight
When it is less than the above range, delamination is likely to occur in the molded product, and it is difficult to obtain sufficient surface appearance of the molded product and strength of the molded product.

The particle size of the polyorganosiloxane rubber-like polymer is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 100 to 400.
nm. This particle size can be controlled by the amount of emulsifier, water, the degree of dispersion when mixed using a homomixer, an ultrasonic mixer, or the addition method of organosiloxane. If the particle size is larger than 500 nm, the gloss is lowered and the appearance is deteriorated.

The polyorganosiloxane rubber-like polymer thus obtained has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 30,000 to 1,000,000, preferably 50,000 to 300,000. is there. If the average molecular weight is too low, the impact resistance of the resulting graft copolymer and the resin composition of the present invention using the same will be poor. If the average molecular weight is too large, the entanglement of the polymer chains is so strong that the rubber elasticity of the rubber particles is lowered and the impact resistance is lowered. The weight average molecular weight can be easily adjusted by changing the condensation polymerization temperature and time when preparing the polyorganosiloxane rubber-like polymer. That is, the lower the condensation polymerization temperature and the longer the cooling time, the higher the molecular weight. In addition, a high molecular weight can be obtained by adding a small amount of a crosslinking agent.

The cross-linking agent used as necessary can be added during the production of the organosiloxane rubber-like polymer. Thereby, the impact resistance of the graft copolymer obtained by using the organosiloxane rubber-like polymer as the rubber-like polymer can be improved. Examples of the cross-linking agent include 3 such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane.
Mention may be made of functional crosslinking agents and tetrafunctional crosslinking agents such as tetraethoxysilane. These cross-linking agents can be used alone or in combination of two or more kinds.
Further, a crosslinked prepolymer obtained by subjecting these crosslinking agents to condensation polymerization in advance may be used as the crosslinking agent. When the crosslinking agent is used, the addition amount thereof is preferably 0.01 to 20% by weight, more preferably 0.02 to 5% by weight, based on the total amount of the organosiloxane, the graft crossing agent and the crosslinking agent. If it exceeds 20% by weight, the flexibility of the polyorganosiloxane rubber-like polymer is impaired, so that the slidability and impact resistance deteriorate.

(D) Hydrogenated rubber The hydrogenated rubber is a hydride of a conjugated diene rubbery polymer. Examples of the hydride of the conjugated diene rubber-like polymer include hydrogenated products of conjugated diene polymers and hydrogenated products of copolymers of conjugated diene and aromatic vinyl compounds, and the latter include conjugated diene compounds. And random copolymers of aromatic vinyl compounds, block copolymers, and the like. The block structure of the hydrogenated product of the block copolymer includes an aromatic vinyl compound polymer block, an aromatic vinyl compound-conjugated diene random copolymer block, and when the conjugated diene compound is butadiene, 1,2 vinyl in polybutadiene. Block with a content of 20% by weight or less, 1,
In the case of a polybutadiene block having a content of 2 vinyl exceeding 20% by weight or a copolymer of polybutadiene and an aromatic vinyl compound, a hydrogenation structure of each block such as a tapered block in which each component gradually increases in addition to a random block included. Examples of the shape of the block copolymer include those having structures of AB type, ABA type, (AB) n type, (AB) nA taper type, radial teleblock type and the like. The hydrogenation rate of the conjugated diene portion in the block copolymer is preferably 95 mol% or more, more preferably 97 mol% or more. If the hydrogenation rate is too low, a rubber-modified thermoplastic resin composition having sufficient weather resistance and discoloration resistance cannot be obtained.

The conjugated dienes used in the production of the block copolymer include 1,3-butadiene, isoprene,
Examples thereof include 1,3-pentadiene and chloroprene, and 1,3-butadiene and isoprene are preferable in order to obtain a hydrogenated diene rubber-like polymer which is industrially applicable and has excellent physical properties. Examples of the aromatic vinyl monomer used for producing the block copolymer include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene and p-styrene. -Tert-butylstyrene, ethylstyrene, vinylnaphthalene, etc.
These are used alone or in combination of two or more. A preferred aromatic vinyl monomer is styrene or an aromatic vinyl monomer containing 50% by weight or more of styrene. The ratio of the aromatic vinyl compound and the conjugated diene compound of this block copolymer can be changed depending on the final performance required of the resin, but the ratio of the aromatic vinyl compound in the copolymer is preferably 10 to 50% by weight. Yes, and more preferably,
It is 13 to 40% by weight. When the amount of the aromatic vinyl monomer is too small, the surface appearance of the molded product of the rubber-modified thermoplastic resin composition is deteriorated, which is not preferable, and when the amount is too large, sufficient impact resistance cannot be obtained.

The following method is mentioned as a typical method for producing the block copolymer used in the present invention. That is, in an inert solvent such as cyclohexane, an organolithium such as n-butyllithium or another alkali metal compound is used as a polymerization catalyst, and tetrahydrofuran or hexamethylphosphoryl is used to adjust the vinyl bond content as necessary. Polar organic compounds such as triamides, thioethers and other tertiary amines are used. The vinyl bond content can also be controlled by the polymerization temperature. A block polymer chain having an active end obtained by the above method,
A branched block polymer can be obtained by coupling with a polyfunctional compound such as silicon tetrachloride or tin tetrachloride. These block polymers can be used alone or in admixture with other block copolymers.

Above, preferred rubbery polymers (a) to
(D) has been described. In any case, the molecular weight distribution of the rubber-like polymer, that is, the weight average molecular weight / number average molecular weight (Mw
/ Mn) is preferably 1.1 to 3, more preferably 1.15 to 2.5. When Mw / Mn exceeds 3, flow marks are generated on the surface of the molded product obtained from the thermoplastic resin composition of the present invention, which causes deterioration of the appearance of the molded product.

These rubber-like polymers may be used alone in the step of polymerizing the rubber-modified resin, or two or more different rubber-like polymers may be mixed and used according to the purpose. By using two or more kinds, a rubber-modified thermoplastic resin composition having high performance can be obtained by utilizing the advantages of each rubber-like polymer.

The rubber-like polymer may be used in combination in an appropriate manner depending on the purpose. For example, it can be used together in the polymerization step for producing a rubber-modified resin, or the rubber-modified resin obtained by polymerizing each rubber separately can be blended and blended with a kneader such as an extruder or a Banbury mixer. You can also do it.

[Monomer used for producing rubber-modified resin] In preparing the rubber-modified resin, examples of the monomer to be polymerized in the presence of the rubber-like polymer include aromatic vinyl compounds and vinyl cyanide compounds. Vinyl monomers such as (meth) acrylic acid ester compounds and maleimide monomers are used. Furthermore, a polyene compound can be used if necessary. Hereinafter, the monomer will be described.

(A ') Aromatic vinyl compound As the aromatic vinyl compound, the same aromatic vinyl compound as used in the production of the block copolymer can be used. These aromatic vinyl compounds may be used alone or in combination of two or more. (B ′) Vinyl cyanide compound Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable. These vinyl cyanide compounds can be used alone or in combination of two or more kinds. (C ') (Meth) acrylic acid ester compound The (meth) acrylic acid ester is preferably an alkyl (meth) acrylate, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl. Alkyl acrylates such as acrylates; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. Preferred are methyl methacrylate and butyl acrylate,
Especially preferred is methyl methacrylate.

Examples of the maleimide compound (d ') include maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like. Are N-phenylmaleimide and N-cyclohexylmaleimide. Examples of the (e ′) unsaturated acid include acrylic acid and methacrylic acid. Examples of (f ') epoxy group-containing unsaturated compound include glycidyl methacrylate and allyl glycidyl ether, and glycidyl methacrylate is preferable. The (g ') hydroxyl group-containing unsaturated compound is 3
-Hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-
4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and the like can be mentioned. It is preferably 2-hydroxyethyl methacrylate. Examples of the (h ') acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like, with maleic anhydride being preferred.

The monomer polymerized in the presence of the rubbery polymer is one or two selected from the above various vinyl monomers.
Used in seeds and above. The preferred monomers used are shown below. (M1) At least one monomer selected from the above (a '), (c'), and (d '). (M2) The above (M1) monomer and the above (b ') (e')
A monomer mixture comprising at least one monomer selected from (f ') and (g'). Regarding the amount of the above-mentioned monomer used, at least one monomer selected from (a ′) (c ′) (d ′) in (M2) is preferably 40 with respect to the total amount of the monomers. ~ 99
%, More preferably 50 to 98% by weight, while at least one monomer selected from (b ′) (e ′) (f ′) (g ′) is based on the total amount of the monomers. Preferably 1 to
It is 60% by weight, more preferably 2 to 50% by weight.
When the amount of the monomer used is within this range, a rubber-modified thermoplastic resin composition having excellent physical properties can be obtained.

Preferred specific combinations of the above monomers are shown below. (1) (a ') and (b'). (2) (a '), (b'), and (c '). (3) (a ') and (c'). (4) (a ') and (d'). (5) (a '), (b'), and (d '). (6) (a '), (b'), (c '), and (d'). (7) (b '), (c'), and (d '). (8) (c ') and (d'). In the above combination, in order to sufficiently obtain the performance of each monomer, the proportion of each monomer is preferably 5% by weight or more based on the total amount of the monomers. In the above combination, the upper limit of component (b ') is preferably 60% by weight, more preferably 5% by weight, based on the total amount of monomers.
It is 0% by weight. However, these compositions can be freely changed in order to express the desired physical properties.

(Production Method of Rubber-Modified Resin) As a production method of the rubber-modified resin of the present invention, a method of radically polymerizing a vinyl monomer in the presence of the above rubber-like polymer can be adopted. As a preferred polymerization operation, after dissolving the rubber-like polymer in an organic solvent,
It is possible to add an emulsifier or the like while stirring at high speed to re-emulsify, and then perform general emulsion polymerization. Also,
Solution polymerization in which a rubbery polymer is dissolved in an organic solvent and then radically polymerized, or bulk polymerization in which a rubbery polymer is dissolved in a monomer and then radically polymerized, and a suspension agent is added after a rubbery polymer is dissolved in a monomer. For example, bulk suspension polymerization in which radical polymerization is performed. The graft ratio of the rubber-modified resin of the present invention is 20 to 20.
0% is preferable, 25-150% is more preferable, 30-110% is still more preferable. If the graft ratio is too high, the rubber elasticity is lost and the impact absorption capacity is reduced, and the impact resistance is reduced. On the other hand, if the graft ratio is too low, a phenomenon such as peeling in layers during molding occurs, the surface appearance of the molded product becomes poor, and the impact resistance decreases. The method for measuring the graft ratio described here is described in the section of Examples.

As mentioned above, the rubber-modified resin is produced by polymerizing the monomer in the presence of the above-mentioned rubber-like polymer. There are formed chemically and / or physically bound (co) polymers of the body and free (co) polymers which are not bound. In the present invention, a mixture of a graft polymer in which a monomer (co) polymer is chemically and / or physically bound to a trunk polymer and a free (co) polymer is referred to as a “graft polymer”.

(Rubber-Modified Resin) The rubber-modified resin of the present invention comprises the above graft polymer alone or (co) polymerizes the monomers used in the graft polymerization in the absence of the rubber-like polymer. The obtained (co) polymer (hereinafter, also referred to as “non-graft polymer”) may be blended with the above graft polymer to form a so-called graft-blend type rubber-modified resin. As the monomer that is (co) polymerized in the absence of the rubbery polymer, the same ones as those described above for the monomer that is polymerized in the presence of the rubbery polymer can be used as they are. The rubber content of the rubber-modified resin of the present invention is preferably 2 to 70% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight.
Is. If the amount of rubber is too small, the shock absorbing ability is insufficient and the impact resistance is lowered, while if it is too large, the molded product has poor appearance.

(Physical Properties of Rubber-Modified Resin) Intrinsic Viscosity [η] (Acetone of Solvent, 30 ° C.)
Is preferably 0.1 to 0.7 dl / g, more preferably 0.2 to 0.65 dl / g, still more preferably 0.25 to 0.6 dl / g. If the intrinsic viscosity is too high, the molding processability of the resin composition of the present invention decreases, the adhesion to the mold is poor, the gloss decreases, and color unevenness occurs in the welded part, resulting in a molded product appearance. Becomes defective. on the other hand,
If it is too low, the impact strength is lowered and it becomes impossible to obtain practical impact resistance.

[Layered Clay Mineral Intercalated with Organic Compound (Organic Layered Clay Mineral)] Next, a layered clay mineral intercalated with an organic compound will be described. As such a clay mineral, a layered inorganic compound having a layered structure and having a property of swelling by incorporating (intercalating) an organic compound as an intercalant between layers can be used. For example, montmorillonite, particularly sodium montmorillonite, magnesium montmorillonite and calcium montmorillonite, and other, kaolinite, non-light, beidellite, vorconscoite, hectorite, saponite,
Phyllosilicates such as smectite clays such as sauconite, sovocaite, stevensite, subinfoldite and vermiculite can be mentioned. Other useful layered inorganic compounds include mica minerals such as illite and mixtures of illite / smectite (such as lectorite, thalosobite, reddite and mixtures of illite with the clay compounds) or attapulgite and sepiolite hydrotalcite-based layered layers. Compounds and the like are included. Among these layered inorganic compounds, smectite clay is preferable, and montmorillonite clay is particularly preferable. These clay minerals are generally obtained by collecting natural minerals and performing a predetermined refining operation. In addition, recently, many kinds of clay such as smectite clay, montmorillonite clay, and mica mineral have been produced by the inorganic synthesis method, and thus they are easily available. These synthetic clays can be used without distinction.

In the present invention, the layered clay mineral is used by intercalating an organic compound so that the interlayer distance is not less than a certain value. In order to form a layered clay mineral swollen sufficiently by intercalation or an exfoliation product induced by intercalation, for example, an organic compound containing an alkyl group having 6 or more carbon atoms is used as an intercalant between layers of the layered clay mineral. It is preferable to incorporate it.

As the intercalating method, various proposed methods can be adopted. For example, in order to bring the phyllosilicate-based clay mineral into contact with the intercalant, the clay mineral is preliminarily mixed with water in an amount of 10% by weight to 20 times its weight, and then the intercalant is brought into contact with the phyllosilicate-based clay mineral. There are ways. Exfoliation of layered clay minerals is promoted by sufficient intercalation.

Thus, the layered clay mineral in which the organic compound is intercalated and the rubber-modified resin can be mixed as they are to obtain the composition of the present invention having desired physical properties.
Further, by radically polymerizing a radically polymerizable monomer in the presence of the intercalated layered clay mineral, it is possible to further increase the interlayer distance of the layered clay mineral and further increase the dispersibility in the resin. It is possible to obtain better results by compounding this with a rubber-modified resin. In this case, for example, an intercalated layered clay mineral is dispersed in an aromatic compound solvent, and an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester compound, etc. are added thereto according to the purpose, and a radical is added. A polymerized product can be used. It is desirable to introduce the polymerizable monomer together with the intercalant into a part or all of the layers of the layered clay mineral.

Examples of the organic compound which can be used as the intercalant in the present invention include organic compounds having a polar group which is easily ionized in the molecule. The polar organic compound causes a strong interaction with the surface of the layer covered with negative ions such as oxygen ions of the smectite clay mineral, and pushes (swells) the layers of the layered clay to expand the organic molecules. It is believed to be intercalated or intercalated in layers. As such an organic compound,
Those having an alkyl group having 6 or more carbon atoms and having a polar group capable of ionizing at the terminal are preferable.
Typically, examples thereof include those having a hydroxyl group or a carboxyl group, aldehydes, amines, and amides. Specific examples of those having a hydroxyl group include aliphatic alcohols such as octyl alcohol and nonyl alcohol, alcohols such as aromatic alcohol substituted with an alkyl group, and phenols.
Further, those having a carboxyl group include linear fatty acids such as stearic acid, palmitic acid, and lauric acid,
Examples include linear alkenoic acid such as oleic acid, dienoic acid such as linoleic acid and polyunsaturated fatty acid such as trienoic acid such as linolenic acid. In addition, examples of aldehydes include hexyl aldehyde. Further, as amines or amides, polar organic compounds having one or more amines or amides, such as alkylamines, aminocycloalkanes and aminocycloalkane substitution products,
Cycloaliphatic diamines, aliphatic amines, alkylaromatic amines, alkyldiarylamines, aliphatic amides, and the like, including primary, secondary, and / or tertiary amines or amides. Among these, amines or amides are preferable, and alkylamine, aliphatic amine, alkylaromatic amine, alkyldiarylamine and the like are particularly preferable. The above organic compounds may be used alone or in combination of two or more.

Preferred amines include 1-hexylamine, 1-heptylamine, 1-octylamine, 1
In addition to primary amines such as -nonylamine, 1-dodecylamine, 1-hexadecylamine, 1-octadecylamine and oleylamine, di-n-dodecylamine, di-n
Secondary amines such as hexadecylamine and di-n-octadecylamine, and further dimethyl-n-octylamine, dimethyl-n-decylamine, dimethyl-n-decylamine, dimethyl-n-tetradecylamine, dimethyl-n- Tertiary amines such as hexadecylamine, dimethyl-n-octadecylamine, dimethyloleylamine, di-n-decylmethylamine, dicocoalkylmethylamine, tri-n-octylamine, tri-n-octylamine, tri-n- Examples thereof include aliphatic amines such as decylamine and tri-n-hexadecylamine. Preferable aliphatic amides include hexylamide, heptylamide, octylamide, nonylamide, lauramide, myristamide, palmitamide, steramide, palmamide, oleamide, linoleamide and the like.

Other polar organic compounds having a nitrile group or a lactam group, pyridines,
Esters, surfactants, ethers and the like can also be used.

[Thermoplastic Resin Composition] The thermoplastic resin composition of the present invention may be a known kneader, for example, various extruders such as a single-screw or twin-screw vent extruder, a Banbury mixer, a kneader, and a roll. It is obtained by kneading each component. A preferred manufacturing method is a method using an extruder. Moreover, when kneading each component, you may knead all components collectively, and you may knead them by a multistage addition system. Regarding the compounding ratio, rubber modified resin 100
It is 0.1 to 50 parts by weight of a layered clay mineral obtained by intercalating an organic compound with respect to parts by weight. Preferably 0.
It is 5 to 30 parts by weight, more preferably 1 to 20 parts by weight, and particularly preferably 1 to 15 parts by weight. When the amount is less than 0.1 parts by weight, the effect of adding the clay mineral does not appear, and when the amount is more than 50 parts by weight, the target scratch resistance can be improved, but the impact strength decreases.

Since the thermoplastic resin composition of the present invention is excellent in scratch resistance, it is useful as a molding material for moldings in which the resin surface is printed by laser marking. The thermoplastic resin composition for laser marking of the present invention is a thermoplastic resin composition comprising the above-mentioned thermoplastic resin composition of the present invention. When the color developed by the laser light is black, the vinyl-based monomer used in the production of the rubber-modified thermoplastic resin is preferably an aromatic vinyl compound and a vinyl cyanide compound as essential components. The content of the vinyl cyanide compound is preferably 20 to 45% by weight, more preferably 20 to 35% by weight. Within this range, a thermoplastic resin composition for laser marking having a high level of molding processability during molding of a molded product, chemical resistance of the molded product, and color development can be obtained. On the other hand, when the color to be developed by laser light is white or chromatic, the vinyl-based monomer used in the production of the rubber-modified thermoplastic resin is preferably an aromatic vinyl compound or (meth) acrylic acid. An ester compound and a vinyl cyanide compound are essential components, and the content of the (meth) acrylic acid ester compound is preferably 5 to 95% by weight, more preferably 10 to 80% by weight. The content of the vinyl cyanide compound can be used within a range that does not deteriorate the color developability of white or chromatic color. When the (meth) acrylic acid ester compound is in this range, excellent color developability is obtained.

By using the laser light absorber, the sharpness of laser marking is improved. The laser light absorber is the rubber-modified resin 10 of the laser marking material.
0 to 5 parts by weight, preferably 0.001 to 5 parts by weight,
It is more preferably 0.005 to 3 parts by weight, and even more preferably 0.005 to 2 parts by weight. When the blending ratio of the laser light absorber is within the above range, the sharpness of laser marking is excellent. On the other hand, if the amount is too large, the appearance and impact resistance of the molded product may deteriorate.

Specific examples of the laser light absorber include black compounds such as carbon black, black iron oxide, titanium black and graphite. The black compound is represented by a wavelength-reflectance curve and is 400 to 700 nm.
The reflectance is 10% or less, preferably 5% or less with respect to the entire wavelength range. That is, this 400-7
As long as it absorbs light in the wavelength range of 00 nm,
It can be used as a black compound. Among the black compounds, carbon black is acetylene black,
Any of channel black, furnace black, ketjen black and the like can be used. The preferred particle size of carbon black is 10 to 80 nm, and more preferably 12 to 40 nm. The smaller the particle size, the better the dispersibility in the resin, and the better the laser marking color development. The preferred specific surface area of carbon black is 20.
~1,500m ² / g, preferably oil absorption 35 to 300
ml / 100g, preferred pH is 2-10. In addition, black iron oxide, which is a black-based compound, is Fe ₃ O ₄ or F.
It is a black iron oxide represented by eO.Fe ₂ O ₃ . The preferred particle size of the black iron oxide is 0.3 to 0.8 μm, more preferably 0.4 to 0.6 μm, and its shape can be spherical, cubic, needle-like, etc. Cubic is preferred. Furthermore, the black compound titanium black is a compound obtained by reducing titanium dioxide. The preferable particle size of titanium black is 0.1 to 60 μm, more preferably 1 to 20 μm.
m. These black compounds may be used alone or in combination of two or more. The black compound as a laser light absorber is blended in the proportions already described for the laser light absorber.

Further, as the laser light absorber, a metal-containing compound other than the following inorganic lead compound (hereinafter simply referred to as "metal-containing compound") can be used instead of or in combination with the above-mentioned black compound. Preferred above-mentioned metals include bismuth, nickel, zinc, calcium,
Copper, titanium, silicon, cobalt, iron and the like can be mentioned, and preferable metal-containing compounds include oxides, carbonates, hydroxides and organic carboxylates of these metals.
Specific examples of the metal-containing compound, bismuth oxide, nickel formate, zinc borate, calcium borate, zinc phosphate, calcium silicate, bismuth hydroxide, basic bismuth carbonate, basic bismuth acetate, nickel hydroxide, Examples thereof include copper oxalate, basic copper carbonate, calcium carbonate, copper thiocyanate, copper citrate, iron oxalate, black iron oxide, and titanium oxide. By blending such a metal-containing compound, more excellent black color development can be obtained. These metal-containing compounds may be used alone or in combination of two or more. The metal-containing compound is blended in the amount proportions already mentioned for the laser light absorber. When combined with the above black-based compound, the amount ratio is applied to the total amount thereof.

[Dye and Organic Pigment] When the thermoplastic resin composition for laser marking of the present invention is irradiated with a laser beam to develop a color other than black, that is, white or yellow, red, blue, green, purple, etc. When coloring in chromatic colors,
Dyes and / or organic pigments can be added to the resin composition. The wavelength-reflectance curve of the dye and / or organic pigment used in the present invention is 400 to 700 nm.
In the wavelength region of, the reflectance partially has a region of 40% or more, preferably 50% or more. The thermoplastic resin composition for laser marking of the present invention, in the portion irradiated with laser light, the dye
Depending on the color of the organic pigment, chromatic colors such as white, yellow, red, blue, green, and purple are brightly colored.

Examples of dyes include nitroso dyes, nitro dyes, azo dyes, stilbene azo dyes, ketoimine dyes,
Examples thereof include triphenylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye, thiazole dye, indamine dye, azine dye, oxazine dye, thiazine dye, sulfur dye, aminoketone dye, anthraquinone dye and indigoid dye.

Specific examples of these dyes include Mord.
ant Green 4, Disperse Yellow
w 14, Disperse Yellow 31, Ac
idYellow 2, Direct Yellow 5
9, Basic Yellow2, Basic Oran
ge 23, Direct Orange 71, Dir
ect Red 28, Acid Red 52, Solv
ent Blue 22, Acid Blue 59, Mo
rdant Blue10, Acid Blue45, V
at Blue 41, Toluidine Maroon, Permanent Red AG, Hansa Yellow G, Hansa Yellow 10G,
Examples include benzidine orange 2G. These are 1
They may be used alone or in combination of two or more.

As the organic pigment, those generally used can be used, but among them, the coordinating metal is calcium, nickel, iron, barium, sodium, copper, molybdenum, cobalt, manganese, zinc, titanium. , Magnesium, potassium and the like are preferable. Specific organic pigments include Watching Red (Ca), Green Gold (Ni), Pigment Green B (Fe), Pigment Scarlet 3B (Ba), Fast Sky Blue (Ba), Phthalocyanine Green (Fe), and Phthalocyanine Blue. (Cu), Brilliant Carmine 6
B (Ca), Bordeaux 10B (Na), Resole Red R (Na), Lake Red D (Na), Brilliant Scarlet G (Ca), Manganese Violet (M
n), cobalt violet (Co) and the like. The metal elements contained in the organic pigment are shown in parentheses after the name of the organic pigment. In addition, these can be used individually by 1 type or in combination of 2 or more types. The dye and the organic pigment may be used alone or in combination.

In the thermoplastic resin composition for laser marking of the present invention, the mechanism of developing a chromatic color is not yet clear, but it is considered as follows. That is, the laser light absorber compounded in the rubber-modified thermoplastic resin,
In the case of carbon black, the laser light is absorbed and the carbon black present in the irradiated area is vaporized. At this stage, the black component in the irradiated portion disappears or decreases. On the other hand, a coloring agent such as a dye or a pigment having a chromatic color, which is present in the irradiated portion, does not absorb the laser light, and therefore remains in the irradiated portion as it is, and the irradiated portion develops a chromatic color derived from the coloring agent. As another explanation of the mechanism, the laser light absorber absorbs laser light and converts the light into heat. The generated heat decomposes and foams the repeating unit derived from the (meth) acrylic acid ester monomer in the rubber-modified thermoplastic resin. Since the foamed portion and the non-irradiated portion have different refractive indexes, the portion does not become black and a chromatic color derived from the coloring agent is developed. As can be seen from such a coloring mechanism, the laser light absorber needs to absorb the laser light, while the colorant needs not to absorb the wavelength of the laser light. Note that titanium black exhibits the white color of titanium dioxide when it is oxidized by light irradiation. Therefore, the color derived from the colorant present in this portion can be recognized. When the dye and the pigment are not mixed and the repeating unit derived from the monomer in the rubber-modified thermoplastic resin is not decomposed or foamed, the portion irradiated with the laser light is carbonized by heat to develop a black color.

Next, in the thermoplastic resin composition for laser marking of the present invention containing the above-mentioned components, the surface of the molded product is irradiated with laser light to cause the irradiated portion to develop black or white or chromatic color. Is possible. Here, as the laser beam, the He-Ne, Ar laser, CO ₂ laser, a gas laser such as an excimer laser, a solid laser such as YAG laser, semiconductor laser, etc. dye laser. Among them, CO ₂
Lasers, excimer lasers and YAG lasers are preferred. The wavelength of the YAG laser light is 1054 nm.

When the molded surface of the thermoplastic resin composition for laser marking of the present invention is irradiated with laser light, the laser light-irradiated portion usually becomes slightly higher than the unirradiated portion. The preferable rising height of this irradiated portion is 1 to 1
Although it is about 00 μm, about 10 to 80 μm is preferable because the laser marking color development and the recognition of the irradiated (character) portion are clear. It is also possible to produce a braille molded product by using this character height.

The thermoplastic resin composition for laser marking of the present invention is a known kneader, for example, various extruders such as a single-screw or twin-screw vent extruder, a Banbury mixer, a kneader, a roll, etc., preferably 160
It can be obtained by kneading each component in the temperature range of ℃ to 300 ℃. At the time of kneading, the respective components may be kneaded at once, or a multi-stage divided kneading method in which after kneading arbitrary components and then adding the remaining components and kneading can be adopted. A preferable kneading method is a method performed by an extruder, and a twin-screw co-rotating extruder is particularly preferable as the extruder. For example, when a graft polymer and a non-graft polymer are used together as a rubber-modified thermoplastic resin, a laser light absorber, a dye and / or a rubber-modified resin prepared by blending the graft polymer and the non-graft polymer in advance are prepared. Alternatively, the pigment and other components may be melt-kneaded. Further, these components may be melt-kneaded at the same time, and further, these components may be melt-kneaded in arbitrary stages in multiple stages. Thus, not only in the case of using a graft polymer and a non-graft polymer in combination, there are various variations in the mixing method of various components, and the resin composition for laser marking of the present invention can be selected appropriately. It can be prepared.

The thermoplastic resin composition of the present invention and the thermoplastic resin composition for laser marking of the present invention can be blended with the following other polymers, if desired. Examples thereof include polyvinyl chloride, polyphenylene ether, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polyvinylidene fluoride and chlorinated polyethylene. These can be used alone or in combination of two or more.

In addition to the thermoplastic resin composition and the thermoplastic resin composition for laser marking of the present invention, an antioxidant such as a hindered phenol-based, phosphorus-based or sulfur-based antioxidant is used depending on the purpose of use of the composition. Ordinarily used additives such as a light stabilizer, an ultraviolet absorber, a lubricant, a colorant, a flame retardant, a reinforcing agent and a filler can be added. The thermoplastic resin composition of the present invention and the thermoplastic resin composition for laser marking thus obtained are injection molding, vacuum molding, sheet molding, extrusion molding, variant molding, foam molding, injection press molding, press molding, It can be molded into various molded products by blow molding or the like. The thermoplastic resin composition of the present invention can be widely used for various applications making use of the above characteristics. For example, it can be used as it is as an exterior material for vehicles, home appliances, office automation equipment, building materials, etc. Can be used. On the other hand, the thermoplastic resin composition for laser marking of the present invention is OA
Buttons, housings for products, home appliances, vehicle applications, etc.
It can be a molded product such as a switch. It can also be used as a building material for sills, window frames, railings, etc. By irradiating the surface of these products with a laser beam, a clear black or white or chromatic color can be developed. Further, the character portion colored by laser marking is more excellent in weather resistance, scratch resistance, and abrasion resistance than the printed character portion, and is therefore far more preferable in practical use than printing.

[0065]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, "part" in an Example means a "weight part" unless there is particular notice.

Various properties of the thermoplastic resin composition were measured and evaluated by the following methods. (1) Charpy impact strength: Notched in conformity with the method of ISO179, unit display kJ / m ² (2) Weather resistance evaluation According to ASTM-D256, a sunshine weatherometer using a carbon arc as a light source (Suga Test Instruments Co., Ltd. WEL- After being exposed to 6XS-DC) for 1,000 hours, the Charpy impact strength was measured and the retention rate (%) was calculated. (Weatherometer test conditions) Black panel temperature 63 ± 3 ° C Chamber temperature 60 ± 5% RH Rain cycle 18 minutes every 2 hours Carbon exchange cycle 60Hr

(3) A black sample prepared by blending a scratch-resistant thermoplastic resin in black was molded by an injection molding machine having a mold clamping pressure of 90 tons to obtain a molded product having a thickness of 3.2 mm. Four pieces of gauze were overlaid on this molded product, and a load of 300 g was placed on the molded product, which was reciprocated 20 times with a cross-cut tester, and the appearance was visually observed. Evaluation is (excellent) ◎ → ○ →
Displayed as Δ → × (poor).

(4) Laser Marking The surface of a plate-shaped molded product was laser-marked using a laser marker (Star Mark 65W; YAG laser light) manufactured by Carl Basel. By irradiating, the color-developing property, the recognizability, and the sharpness of the color-developed portion were visually judged. ⊚: Good (when the character color is clear and has good recognizability) Δ: Slightly inferior (when either the sharpness or the recognizability is inferior)

(5) Measurement of graft ratio A certain amount (x) of the graft copolymer is put into acetone and shaken for 2 hours on a shaker to dissolve the free copolymer. Using a centrifuge, add 15000 r of this solution.
Insoluble matter is obtained by centrifugation at pm for 30 minutes. Next, by vacuum drying, it is dried at 120 ° C. for 1 hour to obtain a dried insoluble matter (y). The graft ratio was calculated by the following formula. Graft ratio (%) = [(y−x × rubber fraction in graft polymer) / (x × rubber fraction in graft copolymer)] ×
100

Component (A): Rubber-modified thermoplastic resin (preparation of ASA resin) 73 parts of styrene (hereinafter abbreviated as St) and 20 parts of acrylonitrile (hereinafter abbreviated as AN) are mixed to prepare a simple mixture. The monomer mixture (I) was prepared. A glass reactor was charged with 20 parts of acrylic rubbery polymer latex (as solid content) and 110 parts of water, and the temperature was raised to 40 ° C. under a nitrogen stream while stirring. When the temperature reached 40 ° C., an aqueous solution prepared by dissolving 0.3 parts of glucose, 1.2 parts of sodium pyrophosphate and 0.01 part of ferrous sulfate in 20 parts of water (hereinafter abbreviated as RED aqueous solution). Of which, t-butyl hydroperoxide (hereinafter abbreviated as BHP) 0.4% in 86% and 30 parts of water.
Part, an aqueous solution in which 2.4 parts of disproportionated potassium rosinate was dissolved (hereinafter, abbreviated as CAT aqueous solution) was charged to a reactor in an amount of 30%, and immediately after that, the monomer mixture (I) and the rest Polymerization was initiated by initiating continuous addition of the CAT aqueous solution of 3 to 3 hours and 3 hours and 30 minutes, respectively. The temperature was raised from the start of polymerization to 75 ° C, and then 7
Hold at 5 ° C. 180 minutes after the start of the polymerization, the remaining 14% of the RED aqueous solution was charged into the reactor, and the polymerization was terminated after maintaining the temperature for 60 minutes. The copolymer latex was coagulated, washed with water and dried to obtain a powdery ASA resin. The polymerization conversion rate was 97% and the graft rate was 79%.

(Preparation of AES resin) Ribbon type stirrer blade,
In a stainless steel autoclave with a volume of 20 liters equipped with a continuous additive additive device, a thermometer, etc., an ethylene / propylene rubber polymer (trade name "EP8 manufactured by JSR Corporation"
4 ") 20 parts, styrene 56 parts, acrylonitrile 2
4 parts and 110 parts of toluene were charged, the internal temperature was raised to 75 ° C., and the contents of the autoclave were stirred for 1 hour to give a uniform solution. Then, 0.45 part of t-butyl peroxyisopropyl carbonate was added, and the internal temperature was further raised to 1
After reaching the temperature of 00 ° C., while maintaining this temperature, the polymerization reaction was carried out at a stirring rotation speed of 100 rpm. Four hours after the polymerization reaction was started, the internal temperature was raised to 120 ° C., and the reaction was continued for another 2 hours while maintaining this temperature, and the reaction was terminated. The graft ratio of the obtained AES resin was 55%. After cooling the internal temperature to 100 ° C., octadecyl-3- (3,3
After adding 0.2 part of 5-di-t-butyl-4-hydroxyphenol) -propionate, the reaction mixture was extracted from the autoclave, the unreacted substances and the solvent were distilled off by steam distillation, and an extruder with a 40 mmφ vent was used. The cylinder temperature was adjusted to 220 ° C. and the vacuum degree was adjusted to 770 mmHg to substantially deaerate volatile components, and the AES resin was pelletized.

(Preparation of Hydrogenated Rubber-Reinforced Thermoplastic Resin (MX Resin)) A hydrogenated block copolymer (trade name “Dinalon, manufactured by JSR Co., Ltd.” was placed in a stainless steel autoclave with an internal volume of 10 liters equipped with a ribbon-type stirring blade. 4600P ")
20 parts, methyl methacrylate 60 parts, styrene 10 parts,
Charge 10 parts of acrylonitrile and 120 parts of toluene,
After dissolving by stirring to obtain a uniform solution, 0.5 parts of t-butylperoxyisopropyl carbonate and 0.1 part of t-dodecyl mercaptan were added, and the temperature was raised while stirring, and after reaching 100 ° C, The polymerization reaction was carried out at a stirring rotation speed of 200 rpm while controlling the temperature constant.
The reaction was completed for 6 hours. The graft ratio of the obtained MX resin was 42%. After cooling to 100 ℃ 2,
After adding 0.2 parts of 2-methylenebis-4-methyl-6-butylphenol, the reaction mixture was extracted from the autoclave, the unreacted substances and the solvent were distilled off by steam distillation, and after finely pulverizing, a 40 mmφ vacuum vent was used. Using an attached extruder (220 ° C., 700 mmHg vacuum), the volatile matter was substantially degassed, and the MX resin was pelletized.

(Preparation of ABS resin) The following (a) component 5
An ABS resin was obtained by mixing 0 parts and 50 parts of the component (b). (A) Component polybutadiene latex (average particle size: 300 nm, gel content: 85% by weight) After emulsion polymerization using 40 parts of styrene, 45 parts of styrene and 15 parts of acrylonitrile, coagulation with magnesium sulfate, washing and drying. Then, a rubber-reinforced resin was obtained. The graft ratio of this rubber-reinforced resin is 60% by weight, and the intrinsic viscosity of the acetone-soluble component measured at 30 ° C. using methyl ethyl ketone as a solvent is 0.45 dl / g.
Met. (B) Component A A having an acrylonitrile content of 26% by weight and an intrinsic viscosity of 0.6 dl / g measured with a methyl ethyl ketone solvent.
S resin

Component (B): intercalated layered clay mineral As the intercalated layered clay mineral, a powder of lipophilic smectite (trade name: Lucentite STN) manufactured by Coop Chemical Co., Ltd. was used.

Examples 1 to 5 and Comparative Examples 1 to 4 Components (A) and (B) shown in Table 1 were used and mixed by the following method. The component (A) was charged into a twin-screw extruder with a vent, the component (B) was added in the middle of the twin-screw extruder, melt-kneaded while devolatilizing, and then extrusion-molded to obtain pellets. Further, the pellets were sufficiently dried and molded into various test pieces by injection molding for evaluation. The results are shown in Table 1.

[0076]

[Table 1]

From the results shown in Table 1, by adding the component (B), the weather resistance and scratch resistance of the rubber-modified thermoplastic resin can be improved, and the impact resistance thereof is not substantially impaired. I understand.

Examples 6 and 7 and Comparative Examples 5 and 6 Components (A) and (B) shown in Table 2 were melt-kneaded by the method shown in Example 1 to obtain a thermoplastic resin composition for laser marking. . With respect to this composition, a test piece of each test was molded and evaluated. Incidentally, in the scratch resistance evaluation method, a black sample mixed with black is molded by an injection molding machine with a mold clamping pressure of 90 tons. Here, the above-mentioned thermoplastic resin composition for laser marking is mold clamped. Pressure 90
It was molded into a scratch-resistant test piece with a ton injection molding machine. The evaluation results are shown in Table 2.

[Table 2]

Examples 6 and 7 are superior to Comparative Examples 5 and 6 in weather resistance, scratch resistance and laser marking property.

[0080]

According to the present invention, since the layered clay mineral in which an organic compound is intercalated is blended with the rubber-modified thermoplastic resin, the weather resistance resin which is required not to be surface-treated such as painting is required. Satisfactory balance of physical properties such as impact resistance, molding appearance, scratch resistance, weather resistance, and moldability. A molded article formed from the thermoplastic resin composition for laser marking of the present invention is excellent in scratch resistance and laser marking property. Therefore, a marking portion colored by laser marking, for example, a character portion, is better than a character portion by printing. Since it has excellent weather resistance and abrasion resistance, it is hard to erase and far better than printing in practical use.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Norifumi Sumimoto             1-18-1 Kyobashi, Chuo-ku, Tokyo Techno             Within Polymer Co., Ltd. F-term (reference) 2C362 CB67                 4F073 AA07 AA13 AA15 AA32 BA06                       BA07 BA13 BA15 BA24 BA26                       BA29 BA34 BA44 BA52 BB01                       BB03 BB08 CA46                 4J002 BN021 BN061 BN071 BN121                       BN141 BN171 BN211 DA078                       DA088 DA118 DE098 DE218                       DH048 DJ006 DJ008 DK008                       EC037 EF057 EG018 EJ017                       EN027 EN037 EP017 FD098                       FD207 FD208

Claims (2)

[Claims] 1. A thermoplastic resin composition comprising 100 parts by weight of a rubber-modified thermoplastic resin and 0.1 to 50 parts by weight of a layered clay mineral in which an organic compound is intercalated. 2. A thermoplastic resin composition for laser marking, comprising the thermoplastic resin according to claim 1.