KR100321869B1 - Mat Thermoplastic resin composition and Laminate therefrom, Matting agent therefore, and Method for matting thermopl-astic resin - Google Patents

Abstract

In the present invention, in order to obtain a thermoplastic resin composition having good quenchability even without adding a quencher or post-processing, 0.5-80% by weight of (meth) acrylic acid hydroxy alkyl ester having 1 to 8 carbon atoms of alkyl group and carbon number of alkyl group to thermoplastic resin 10-99% by weight of methacrylic acid alkyl ester of 1-13, 0-79% by weight of acrylic acid alkyl ester having 1-8 carbon atoms of alkyl group, 0-70% by weight of vinyl aromatic monomer and 0-20% by weight of monoethylenically unsaturated monomer A thermoplastic resin composition, a resin laminate and a thermoplastic resin having excellent mat properties by using as a mat a copolymer prepared by selectively polymerizing a non-crosslinkable monomer mixture comprising a copolymerizable crosslinkable monolayer having two or more double bonds in a molecule. To provide a mat agent, the present invention is to reduce the cost of the physical properties due to the addition of the matting agent or the post-processing It can have the effect to obtain the thermoplastic resin composition.

Description

Mat Thermoplastic resin composition and Laminate therefrom, Matting agent therefore, and Method for matting thermopl-astic resin

The present invention relates to a thermoplastic resin composition having excellent mat properties, a thermoplastic resin laminate, a mat for thermoplastic resin, and a matting method of thermoplastic resin.

In general, molded articles of thermoplastic resins such as acrylic resins, polyvinyl chloride resins and ABS resins have a gloss, and this gloss becomes an important characteristic depending on the application. However, in some cases, such gloss is not necessary, and in many cases, matte or cloudy colors are preferred.

Conventional methods for matting thermoplastic resins can be broadly divided into embossed or matte finishes and methods of adding inorganic or organic matting agents. However, embossed or matte finishes can be used in terms of productivity and manufacturing cost. If the fall and the mat effect is insufficient to require the fabrication (fabrication) of the resin, while it is unsuitable, there is an advantage that the degradation of the physical properties of the resin is very small. On the contrary, the method of adding the inorganic or organic mat agent has a large decrease in the physical properties of the resin while lowering the productivity, but also has the advantage of being able to adjust the finishing range of the mat and easily use it even when a paving is required. In particular, when an inorganic material such as silica gel is used as a mat agent, there are closed ends in which the impact resistance, tensile strength and elongation of the resin are greatly reduced.

On the other hand, in addition to the conventional method described above, another method is disclosed in Japanese Patent Laid-Open No. 56-36535, which method uses an organic material, in particular a polymer mat agent.

More specifically, a crosslinkable polymer having an average particle diameter of 35 to 500 µm prepared by suspension polymerization is used. However, the method using the polymer mat agent is inferior in the mat effect, but the impact resistance and the decrease in tensile strength and elongation are very small.

Accordingly, an object of the present invention is to solve the above problems and to provide a thermoplastic resin having excellent mat properties.

The present inventors have found that by copolymerizing copolymer (B) composed of acrylic acid hydroxyalkyl ester and methacrylic acid hydroxyalkyl ester units or acrylic acid hydroxyalkyl ester or methacrylic acid hydroxyalkyl ester units, It has been found that the mat effect on seed thermoplastics can be greatly improved.

The present invention relates to acrylic acid hydroxyalkyl ester and methacrylic acid hydroxyalkyl ester (b-1) having an intermediate portion of thermoplastic resin (A) 100 and an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 13 carbon atoms. Methacrylic acid alkyl ester (b-2) having from 10 to 99% by weight, acrylic acid alkyl ester having from 1 to 8 carbon atoms (b-3) 0 to 79% by weight, vinyl aromatic monomer (b-4) 0 to 70 Monomer mixture comprising a monomer mixture (B-1) mixed with 0% to 20% by weight of a monoethylenically unsaturated monomer (b-5) and a copolymerizable crosslinkable monomer (B-2) having two or more double bonds in a molecule. (B-1) 0.1 to 40 parts by weight of a copolymer (B) prepared by polymerization in an amount of 0 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition (I) having excellent mat properties. .

In addition, the present invention is a thermoplastic resin composition (I) composed of 100 parts by weight of a thermoplastic resin (A) and 0.1 to 40 parts by weight of the copolymer (B) described above to form the surface of the thermoplastic base resin (E) and the base resin (E). It relates to a thermoplastic resin laminate having excellent mat properties composed of).

Moreover, this invention relates to the mat agent for thermoplastic resins comprised from said copolymer (B). Moreover, this invention relates to the mat method of the thermoplastic resin (A) which blended 0.1-40 weight part of said copolymers (B) with respect to 100 weight part of thermoplastic resins (A).

As the thermoplastic resin (A) used in the present invention, any of the thermoplastic resins commonly used may be used, but acrylic resins, polyvinyl chloride resins and ABS resins are preferred, and acrylic resins are more preferred.

"Acrylic resin" used in the present invention means an acrylic resin and methacryl resin.

Hereinafter, the monomer used for a copolymer (B) is demonstrated. Acrylic acid hydroxyalkyl esters and methacrylic acid hydroxyalkyl esters or acrylic acid hydroxyalkyl esters or methacrylic acid hydroxyalkyl esters include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,3 -Dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate, of which 2-hydroxyethyl methacrylate is particularly preferred.

As for the usage-amount of acrylic acid hydroxyalkyl ester and methacrylic acid hydroxyalkyl ester, 0.5 to 80 weight% is preferable. When the crosslinkable monomer is not used, when the amount of ester added is less than 1% by weight, the effect of improving the mat properties is insufficient. When the amount of ester added when the crosslinkable monomer is used is less than 0.5% by weight, the effect of improving the mat properties is not satisfactory. . In addition, when the crosslinkable monomer is not used, if the amount of the ester added exceeds 80% by weight, the surface state of the final product is poor, and when the amount of the hydroxyalkyl ester is used exceeds 50% when the crosslinkable monomer is used, the final product Surface condition is poor. Therefore, when the crosslinkable monomer is not used, the amount of ester is preferably used to improve the mat property in the range of 5 to 50% by weight, whereas the amount of ester is 1 to 40% by weight when using the crosslinkable monomer. It is desirable for improving the sex.

Suitable methacrylic acid esters are lower methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, with methyl methacrylate being particularly preferred. The amount of methacrylic acid ester used is in the range of 10 to 99% by weight, and when the crosslinkable monomer is not used, the amount of methacrylic acid used is preferably 30 to 85% by weight. On the other hand, when a crosslinkable monomer is used, the amount of methacrylate used is preferably in the range of 15 to 70% by weight.

The acrylic acid alkyl ester can be used in the range of 79% by weight, preferably 0.5 to 40% by weight, more preferably 5 to 25% by weight. The acrylate is preferably a lower acrylic acid alkyl ester such as methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.

The aromatic vinyl monomer can be used in the range of 70% by weight. When no crosslinkable monomer is used, the aromatic vinyl monomer is preferably used in an amount of 0 to 40% by weight, preferably 0 to 20% by weight. On the other hand, when a crosslinkable monomer is used, it is preferable to use 10-60 weight% of aromatic vinyl monomers, More preferably, 15-55 weight%. Aromatic vinyl monomers include styrene, vinyltoluene, α-methylstyrene, halogenated styrene and the like, of which styrene is most preferred.

In addition, the monoethylenically unsaturated monomer can be used in the range of 20% by weight, preferably 0 to 10% by weight based on the copolymer (B) of the present invention. In particular, conventional monomers can be used as unsaturated monomers, for example methacrylic acid, fumaric acid, maleic acid and copolymerizable carboxylic acids and their esters (methacrylic acid alkyl esters with alkyl groups having 1 to 13 carbon atoms and carbon atoms). Acrylic acid alkyl esters having alkyl groups of 1 to 8), vinyl halides such as vinyl chloride and vinyl bromide, vinyl esters such as vinyl acetate, acrylonitrile and the like. As the crosslinkable monomer (B-2), a compound containing two or more unsaturated bonds is used. In particular, allyl groups including crosslinkable monomers such as allyl methacrylate, triallyl cyanurate and triallyl isocyanurate, unsaturated carboxylic acids of alkylene glycols such as ethylene glycol dimethacrylate, propylene Unsaturated alcohol ethers of alkylene glycols such as glycol diallyl ether and polyhydric benzenes such as divinyl benzene are included, of which allyl methacrylate is preferred.

The crosslinkable monomer has at least two or more unsaturated bonds, and at least one of them is preferably an allyl group. By using the crosslinkable monomer including the allyl group described above, it is possible to produce a copolymer (B) having a suitable density distribution of the crosslinkable monomer in the copolymer (B). The addition amount of a crosslinkable monomer shall be 0-5 weight part with respect to 100 weight part of noncrosslinkable monomers. It is most preferable to use a crosslinkable monomer from a viewpoint of mat property improvement, but mat property can fully be improved even if a crosslinkable monomer is not used. On the contrary, when the crosslinkable monomer is used in excess of 5% by weight, the surface conditions of the final polymer will be poor.

The method for producing the copolymer (B) is not particularly limited, but the suspension polymerization method is preferable. As an initiator of suspension polymerization, the initiator used for normal suspension polymerization can be used, and organic peroxide and an azo compound are included here.

As a stabilizer for suspension polymerization, stabilizers used in conventional suspension polymerization may be used, and organic colloidal polymer materials, inorganic colloidal polymer materials, inorganic fine particles, or a combination of these materials and a surfactant may be used.

In the present invention, a polymerization rate regulator such as mercaptan can be used, and in most cases, it is preferable to use a polymerization rate regulator to control the molecular weight.

Suspension polymerization is usually carried out by forming a water-soluble suspension of a polymerization initiator and a monomer in the presence of a suspension polymerization stabilizer, using a polymer dissolved in a monomer, or partially performing bulk polymerization without the addition of a crosslinkable monomer. Suspension polymerization is carried out by adding a monomer and a suspension polymerization stabilizer.

In the case of using a crosslinkable monomer, it is effective that the particle diameter of the resulting polymer particles is 5 to 500 m, preferably 40 to 250 m. When the average particle diameter is smaller than 5 mu m, the mat properties are insufficient, and when the average particle diameter is larger than 500 mu m, the surface of the final molded product becomes rough and it is difficult to obtain uniform mat properties.

The blend amount of the copolymer (B) thus produced is in the range of 0.1 to 40 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin (A). When not using a crosslinkable monomer, in order to obtain the excellent mat property, it is preferable to add 2.0 weight part or more of copolymers (B). When using a crosslinkable monomer, it is preferable to use 1.0 weight part or more from a matt effect.

Among various acrylic resins, the acrylic polymer (C) having a multi-layer structure and the acrylic copolymer (D) defined as follows are particularly excellent in terms of improving matte properties.

The structure of the acrylic polymer (C) (hereinafter referred to as "multilayer polymer") having a multilayer structure and the monomers used in the production of the acrylic polymer (C) are as follows.

The acrylic acid alkyl esters having 1 to 8 carbon atoms of alkyl group forming the innermost polymer (Ca) are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and n-octyl acryl. Is made of rate. Such acrylates are used alone or in combination and preferred are low Tg esters. Methacrylic acid alkylesters whose esters are used to make the innermost polymer (C-a) include methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. These acrylates can be used alone or in combination. Such acrylic or methacrylic acid alkyl esters (C-al) are used in the range of 80 to 100% by weight. In the continuous polymerization step, it is most preferable to use the same acrylic or methacrylic ester, but heterogeneous esters or two or more esters may be used in the continuous polymerization step depending on the final purpose.

As the copolymerizable monomer (C-a2) having one double bond, acrylic or methacrylic monomers such as acrylic acid higher alkyl ester, acrylic acid lower alkoxy ester, acrylic acid cyanoethyl ester, acrylamide, acrylic acid and methacrylic acid are preferable. Is 0 to 20% by weight. Styrene, alkyl-substituted styrene, acrylonitrile or methacrylonitrile do not exceed 20% by weight in the component (C-a).

Polyfunctional monomers (C-a3) include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and propylene glycol dimethacrylate. Dimethacrylic acid alkylene glycol esters are preferred, and polyvinylbenzene and diacrylic acid alkylene glycol esters such as divinylbenzene and trivinylbenzene can be used. These monomers work effectively to form crosslinks in the layers in which they are contained, but they do not work to form bonds between one layer and another, and even the innermost polymer even when no multifunctional monomer (C-a3) is used at all. As long as the graft binder is present in the component (Ca), a polymer having a stable multilayer structure can be produced. However, multifunctional monomers can optionally be used depending on the conditions, for example where high hot strength is strictly required, and the multifunctional monomers find 0 to 10% by weight.

Graft binders include allyl esters, methallyl esters or crotyl esters of α, β-unsaturated carboxylic acids or dicarboxylic acids, and allyl esters of acrylic acid, methacrylic acid, maleic acid or pmaric acid. Is preferred, and in particular, allyl methacrylate has an excellent effect. Triallyl cyanorate and triallyl isocyanate are also effective. Such graft crosslinkers act as conjugated unsaturated bonds in esters faster than allyl groups, metalyl groups or crotyl groups on chemical bonds.

On the other hand, allyl group, metallyl group or crotyl group, the polymer polymerization of the continuous layer to effectively produce a graft bond between adjacent layers is effective.

The amount of the graft crosslinking agent is very important, but it is ideal to use 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total amount of the components (C-al) to (C-a3). When the amount of use is less than 0.1 part by weight, the amount of crosslinking is lowered. When the amount of use is more than 5 parts by weight, the amount of reaction with the crosslinking elastomer produced by the second step of polymerization increases, so that the crosslinked rubber having a two-layer elastic structure, which is a characteristic of the present invention This causes the elasticity of the to fall.

The amount of the innermost polymer (C-a) in the multilayer polymer (C) of the present invention is 5 to 35% by weight, preferably 5 to 15% by weight, and preferably smaller than the amount of the crosslinked elastomer (C-b). The crosslinked elastomer (C-b) constituting part of the multilayered polymer (C) provides a polymer (C) having rubber elasticity. The components (C-b1) to (C-b3) constituting the crosslinked elastomer (C-b) and the crosslinking binder may each use the same monomers as those used for the innermost polymer. The component (C-b1) is 80 to 100% by weight, the component (C-b2) is 0 to 20% by weight, the component (C-b3) is 0 to 10% by weight, and the graft crosslinking agent is (C-b1) to (C -b3) find 0.1-5 weight part with respect to 100 weight part of total amounts of a component.

The amount of the elastic polymer (C-b) in the multilayer polymer (C) of the present invention is 10 to 45% by weight, and in this case, more than the amount of the innermost polymer (C-a) is preferable.

In addition, in order to obtain a final polymer having excellent solvent resistance and water-whitening resistance, two-layer crosslinked rubbers having a gel content and an swelling degree of 85% or more and 3-13%, respectively, measured by the following method An elastic body was found and the present invention was completed.

[Measuring method of gel content and degree of expansion]

A sample of the two-layered crosslinked rubber elastomer was taken according to the method of JIS K-6388 and impregnated with methyl ethyl ketone (hereinafter referred to as MEK) at 25 ° C. for 48 hours to inflate the sample, remove the MEK, and then bury it in the sample polymer. Wipe off the MEK, weigh the polymer, dry it completely in a vacuum dryer, evaporate the MEK, and record the absolute dry weight of the polymer when the weight of the polymer is constant. do.

The outermost polymer (C-c) constituting a part of the multilayer polymer (C) of the present invention imparts the moldability and mechanical properties of the multilayer polymer (C).

As the components (C-c1) to (C-c2) constituting the outermost polymer (C-c), the same monomers as those used for the components (C-a1) and (C-a2) can be used. (C-cl) and (C-c2) components use 51-100 weight% and 0-49 weight%, respectively. In addition, the Tg of the outermost polymer (C-c) itself needs to be 60 ° C or higher, preferably 80 ° C or higher, in order to obtain a final polymer having excellent solvent resistance and water resistance. If the Tg of the (C-c) polymer is less than 60 ° C, even if the gel content of the final polymer is 50% or more, the final polymer having excellent solvent resistance and water resistance may not be produced.

Content of outermost layer polymer (C-c) of the multilayer polymer (C) of this invention is 10 to 80 weight%, Preferably it is 40 to 60 weight%. The multilayer polymer (C) is composed of an innermost polymer (Ca), a crosslinked elastic polymer (Cb) and an outermost polymer (Cc) as a basic structure, and an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms (C-dl). ) Is 10 to 90% by weight, methacrylic acid alkyl ester having 1 to 4 carbon atoms (C-d2) 90 to 10% by weight, copolymerizable monomer (C-d3) having a double bond 0 to 20% by weight %, The multifunctional monomer (C-d4) is from 0 to 10% by weight, the graft crosslinking agent is made from a mixture consisting of 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the (C-d1) to (C-d2) monomer At least one of (Cd), the intermediate layer (Cd) is laminated between the crosslinked elastic polymer (Cb) and the outermost layer polymer (Cc), the amount of the alkyl acrylate ester in the polymer is the outermost layer on the crosslinked elastomer (Cb) side Slowly decrease towards polymer (Cc). As the (C-dl) to (C-d4) component and the graft crosslinking agent, the same monomers as those used for the innermost polymer (C-a) can be used. The graft crosslinking agent used in the intermediate layer was needed to closely bond adjacent polymer layers to each other to obtain a final polymer having excellent properties.

The amount of intermediate layer (C-d) in the multilayer polymer of the present invention is 5 to 35% by weight. If it is less than 5% by weight, the interlayer loses its function, and if it exceeds 35%, the properties of the final polymer will be out of balance.

The multilayer polymer (C) of the present invention is composed of layers of polymer (C-a), polymer (C-b), polymer (C-c) and polymer (C-d). In order to impart excellent mat properties to the thermoplastic resin composition composed of the multilayer polymer (C) and the copolymer (B) having a hydroxyl group, the gel content of the multilayer polymer (C) must be 50% or more. In addition, in order to impart excellent solvent resistance and water resistance to the multilayer polymer (C), the gel content of the multilayer polymer (C) should be 50%, especially 60% or more. The term "gel content" as used herein refers to the total amount of graft components from the two-layered crosslinked elastomer itself and the middle layer (C-d) and the outermost polymer (C-c) towards the crosslinked rubber elastomer. In particular, the term "gel content" refers to the weight percent of the insoluble component measured by dissolving 1 wt% of the multilayer polymer in MEK, and then standing for 1 day and centrifuging at 16,000 r.p.m. for 90 minutes. This insoluble component refers to the weight of the two-layer crosslinked rubber elastomer and the graft layer. The weight percent of this insoluble component can be replaced by the Grap rate, and since the polymer has a special structure, the term "gel content" is used as a reference for the amount of graft in the present invention.

When salting out the polymer emulsion of the present invention, the amount of metal remaining in the final polymer should be less than 500 ppm.

The method for producing the multilayer polymer (C) is not particularly limited, but a multistage polymerization method using an emulsion polymerization technique is most suitable, for example, a polymerization system at the time of polymerizing the outermost layer polymer (Cc) during emulsion polymerization. The multilayer polymer (C) can be produced by emulsion-suspension polymerization by changing to a suspension polymerization system.

Next, the composition of acrylic polymer (D) and its manufacturing method are demonstrated concretely.

The acrylic polymer (D) is 0.1 to 20% by weight of the thermoplastic resin (D-1), 5 to 80% by weight of the rubber-containing polymer (D-2) and 0 to 0% of the other thermoplastic polymer (D-3) based on 100% by weight of the total amount. It consists of 93.9 weight%, and polymer (D-1)-(D-3) are explained in full detail next. The thermoplastic polymer (D-1) in the acrylic polymer (D) is prepared by the polymerization of 50-100% by weight of methyl methacrylate and 0-50% by weight of at least one other copolymerizable vinyl monomer and has a reduced viscosity of at least 0.1 l / g ( reduced viscosity: measured by dissolving 0.1g of polymer in chloroform at 100 ℃ and 25ml). The polymer (D-1) plays an important role in film formation. If the reduced viscosity of the polymer is less than 0.1 l / g, a film with good thickness accuracy cannot be produced. Usually the reduced viscosity is more than 0.1 l / g and less than 2 l / g, preferably 0.2 to 1.2 l / g. As the vinyl monomer copolymerizable with methyl methacrylate in the thermoplastic polymer (D-1), acrylic acid alkyl esters, methacrylic acid alkyl esters, vinyl aromatic compounds and vinyl cyanide may be used.

It is preferable that a thermoplastic polymer (D-1) is manufactured by emulsion polymerization, and the produced polymer is collect | recovered in powder form by the normal post-processing continuous emulsion polymerization method. The rubber-containing polymer (D-2) has a function of providing excellent impact resistance and elongation to the resin composition, and the polymer (D-2) is a graft copolymer having a multilayer structure, and contains an acrylic acid alkyl ester as the rubber component. In addition, the polymer (D-2) is a component necessary for improving the mat property.

The rubber-containing polymer (D-2) polymerizes 10 to 2000 parts by weight of one monomer, or 50 to 99.9 weight percent of an alkyl acrylate ester, 0 to 40 weight percent of other copolymerizable vinyl monomers and 0.1 to 10 weight percent of a copolymerizable crosslinkable monomer. Obtained by polymerizing a monomer mixture consisting of 10 to 2000 parts by weight of a monomer mixture consisting of 0 to 50% by weight of a vinyl monomer copolymerizable with 50 to 100 parts by weight of methacrylic acid ester in at least one step in which at least one 100 parts by weight of the elastic copolymer obtained by polymerizing the monomer mixture is polymerized. do.

The acrylic acid alkyl ester used here has an alkyl group having 1 to 8 carbon atoms, of which butyl acrylate and 2-ethylhexyl acrylate are preferable. Less than 40% by weight of other copolymerizable vinyl monomers may be copolymerized in preparing the elastic copolymer. As the vinyl monomer used here, methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate and cyclohexyl methacrylate, styrene and acrylonitrile are preferable.

In addition, copolymerizable crosslinkable monomers may be used. Crosslinkable monomers used include ethylene glycol dimethacrylate, butane dioldimethacrylate allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene , Diallyl maleate, trimethylol triacrylate, allyl cinnamate, and the like.

As monomers to be grafted to the elastomeric copolymer, more than 50 weight percent of methacrylic acid alkyl esters are used, and in particular, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, Cyclohexyl methacrylate is included. In addition, less than 50% by weight of other copolymerizable vinyl monomers may be used. The vinyl monomer is not particularly limited, but acrylic esters such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, styrene, acrylonitrile and the like are used.

The amount of the monomer mixture to be graft copolymerized is 10 to 20 parts by weight, preferably 20 to 200 parts by weight with respect to 100 parts by weight of the elastic copolymer, and the rubber-containing polymer (D-2) of the present invention is prepared by conventional emulsion polymerization method. Are manufactured. In the polymerization, a chain transfer agent and a polymerization aid may be used. Conventional compounds may be used as the chain transfer agent, but mercaptan is preferably used.

The rubber-containing polymer (D-2) obtained in order to improve the mat property is used in an amount of 5 to 80% by weight, preferably 30% by weight, more preferably 50% by weight, based on the acrylic polymer (D).

The thermoplastic polymer (D-3) used in the present invention is 50 to 99.9% by weight of methacrylic acid ester having 1 to 4 carbon atoms, 0.1 to 50% by weight of acrylic acid ester having 1 to 8 alkyl groups and copolymerized therewith It is made from 0 to 50% by weight of vinyl monomers possible, and the reduced viscosity (measured by dissolving 0.1 g of polymer in 100 ml of chloroform at 25 ° C.) is less than 0.1 l / g.

Methacrylic acid esters used as the thermoplastic polymer (D-3) include methyl methacrylate, ethyl methacrylate and butyl methacrylate, of which methyl methacrylate is most preferred. Acrylic esters include methyl acrylate, ethyl acrylate and butyl acrylate. The amount of acrylic ester used is 0.1 to 50% by weight, preferably 0.5 to 40% by weight. As other copolymerizable vinyl monomers, conventional compounds may be used.

Although the manufacturing method of a thermoplastic polymer (D-3) is not specifically limited, It can manufacture by a conventional suspension polymerization method, emulsion polymerization method, or block polymerization method. In the polymerization, chain transfer agents may be used as well as other polymerization aids. Conventional compounds may be used as the chain transfer agent, but mercaptans are preferred.

It is a characteristic of the present invention that the haze of the thermoplastic resin product can be improved when the acrylic multilayer polymer (C) or acrylic polymer (D) is used as the thermoplastic resin (A). In one application, an acrylic polymer is laminated to a polyvinyl chloride resin to improve the weather resistance of the polyvinyl chloride resin when the acrylic resin is used as a film. In this case, it is necessary to have a low haze value so that the pattern printed on the polyvinyl chloride is clearly seen through the acrylic film. When the mat agent known from Japanese Patent Application Laid-Open No. 56-36535 is used, the improvement of the haze value is insufficient, while the use of the thermoplastic resin composition (I) of the present invention reduces the haze.

The mixing method of the thermoplastic resin composition (I) is generally a method of simultaneously shearing and compressing a polymer blend through a screw-type extruder, a method of mixing a polymer blend between hot rolls, and a banbury mixer. Any suitable method of mixing the polymer blend in the same high temperature high shear type mixer can be used.

The thermoplastic resin composition (I) of the present invention may also contain a general chemical aid, for example, stabilizers, lubricants, shock absorbers, plasticizers, antifoaming agents, fillers and pigments. The resulting thermoplastic resin composition (I) can be easily molded into the form of a film or sheet by conventional methods such as the tee-die method, the inflation method, the calender method and the extrusion method.

Moreover, in this invention, a thermoplastic resin laminated body excellent in mat property can be manufactured by laminating | stacking a thermoplastic resin composition (I) on the surface.

As the base material on which the thermoplastic resin composition (I) is laminated, an ordinary thermoplastic resin can be used, and among them, an acrylic resin, a polycarbonate resin, a polyvinyl chloride resin or an ABS resin is preferable.

The manufacturing method of the thermoplastic resin laminated body which uses thermoplastic resin composition (I) and has the outstanding mat property is not specifically limited, A conventional method can be employ | adopted. In particular, one polymer is first formed into a film, a solution containing another polymer is sprinkled on the film, and then a solvent is evaporated. In addition, a co-extrusion method using an extruder and an extrusion lamination are preferred. Method, a heating lamination method using a high temperature roll, etc. are mentioned.

Moreover, an intermediate | middle layer is formed between the thermoplastic resin composition (I) of a surface, and a thermoplastic resin, and a thermoplastic resin laminated body can also be manufactured. In addition, when printing on the thermoplastic resin composition (I) of the laminate, printing is easy and the design effect is also remarkably improved.

When using a conventional mat agent, the mat properties were insufficient, but according to the present invention, the use of the copolymer (B) as a mat material improved the mat property of the thermoplastic resin composition without damaging the surface state.

Hereinafter, the present invention will be described in detail by way of examples and comparative examples. This invention is not limited to an Example.

In the Examples, "parts" means "parts by weight" unless otherwise specified. In addition, the characteristic of the resin composition shown by the Example was measured and evaluated by the following method.

① Surface gloss at 60 ℃: Measured by GM-26D gloss meter manufactured by Murakami Color Research Institute of Japan.

② Surface state: Measure the surface state (roughness and smoothness) through visual observation of the dispersion state of the mat agent.

○: excellent

△: normal

×: defective

③ Izod impact strength (kgcm / cm 2): measured according to ASTM D-256 (V-notch).

(4) Haze: The resin composition was molded into a film having a thickness of 50 µm and immersed in soapy water until the film surface was smoothed, and then measured by SEP-H-SS haze system (manufactured by Nippon Precision Optical Co., Ltd.).

Example 1

(1) Preparation of Copolymer (B):

The following mixture is placed in a reactor equipped with a stirrer, a reflux condenser and a nitrogen gas injector.

The air in the reactor is sufficiently replaced with nitrogen gas, the temperature in the reactor is heated to 75 ° C., and polymerization is carried out while stirring with nitrogen gas. After 3 hours the temperature in the reactor is raised to 90 ° C. and the temperature is maintained for 45 minutes to complete the polymerization. The reaction product was dehydrated and evaporated to give copolymer (B).

(2) Preparation of an acrylic polymer having a multilayer structure (C):

250 parts of water, 2 parts of sodium salts of sulfosuccinic acid ester and 0.05 parts of sodium formaldehyde sulfoxylate were added to a polymerization tank equipped with a cooler, and the mixture was sufficiently stirred under a nitrogen gas, 1.6 parts of methyl methacrylate, 8 parts of butyl acrylate, 1, 0.4 part of 3-butylene glycol dimethacrylate, 0.1 part of allyl methacrylate and 0.04 part of cumene hydroperoxide were added thereto, the temperature was raised to 70 ° C, and the reaction was continued for 60 minutes to polymerize the innermost layer polymer (Ca). Completed Mixture for forming crosslinked elastomer (Cb) consisting of 1.5 parts of methyl methacrylate, 22.5 parts of butyl acrylate, 1.0 part of 1,3-butylene glycol dimethacrylate, 0.25 parts of allyl methacrylate, and 0.05 parts of cumene hydroperoxide Was added and the polymerization was completed to obtain a 2-layered cross-linked rubber-like elastic polymer. The resulting two-layered crosslinked rubber elastomer was measured for swelling and gel content according to the method described above, and the measured value was 10% for expansion and 90% for gel.

The mixture for the intermediate layer polymer (Cd) consisting of 5 parts of methyl methacrylate, 5 parts of butyl methacrylate and 0.1 part of allyl methacrylate was reacted, and finally, the outermost polymer consisting of 52.25 parts of methyl methacrylate and 2.75 parts of butyl acrylate. The mixture for (Cc) was reacted to complete the polymerization.

The polymer emulsion obtained using 5 parts of calcium chloride with respect to 100 parts of polymer was salted out, washed with water, and dried to obtain a polymer having a multilayer structure (C).

The amount of calcium remaining in the final polymer composition was about 200 ppm.

(3) Preparation of the mat thermoplastic resin composition (1):

10 parts of the copolymer (B) prepared by the method (1) above and 100 parts of the polymer having the multilayer structure (C) prepared by the method (2) and (2) were extruded at 240 ° C. with a twin screw extruder to obtain a pellet. After drying the obtained pellet, the film of about 50 micrometers thickness was shape | molded by the tee-die method. 60 degreeC surface gloss and surface state of the molded film were measured, and the result is shown in Table 1.

Example 2-Example 8

The composition of the polymer (B) and the blended copolymer (B) having the multilayer structure (C) were the same as in Example 1 except that the compositions were changed as shown in Table 1, and the results are shown in Table 1.

Example 9

(1) Preparation of Copolymer (B):

The ratio of 10 parts of methyl acrylate and various kinds of methacrylic acid hydroxyalkyl esters was changed and mixed as shown in Table 2. Each mixture was dissolved in 0.35 parts of n-octyl mercaptan and introduced into the reactor, followed by 0.35 parts of lauroyl peroxide as a polymerization catalyst, and methyl methacrylate as a suspending stabilizer and sulfoethylsodium salt of methacrylic acid. 0.02 parts of copolymer, 0.354 parts of sodium sulfate and 145 parts of deionized water were added as a dispersion medium. After completion of the polymerization at 70 ° C. and the temperature inside the reactor reached a peak, the reaction product was allowed to stand at 95 ° C. for 30 minutes, followed by cooling and filtration. , Washed and dried to prepare a copolymer (B) having a hydroxyl group.

(2) Preparation of Thermoplastic Polymer (D-1):

200 parts of deionized water, 1 part of potassium oleate and 0.3 part of potassium persulfate were put as an emulsifier, and 40 parts of methyl methacrylate, 10 parts of n-butyl acrylate, and 0.005 part of n-octyl mercaptan were added. The air in the reactor was replaced with nitrogen gas, and the contents in the reactor were heated at 65 ° C. for 3 hours while stirring with a nitrogen stream to complete the polymerization. Then, a mixed solution consisting of 48 parts of methyl methacrylate and 2 parts of n-butyl acrylate was added to the reactor over 2 hours, and then left at the same temperature for 2 hours to complete the polymerization. In order to salt the resulting polymer, an aqueous sulfuric acid solution was added to the polymer latex, followed by dehydration and drying to obtain a polymer in a split phase. The converted viscosity (η sp / c) of the obtained polymer was 0.38 L / g.

(3) Preparation of rubber-containing polymer (D-2):

The reaction mixture of the following structure was put in the reactor, and it stirred under heating for 4 hours in 50 degreeC nitrogen gas presence, and completed superposition | polymerization, and obtained polymer latex.

100 parts of polymer latex (solids) are removed from the reactor and the air in the reactor is replaced with nitrogen gas while stirring and the mixture is heated to 80 ° C. or higher. An aqueous solution of 0.125 parts of sodium formaldehyde sulfoxylate and 2 parts of deionized water was added and a mixture of 60 parts of methyl methacrylate, 0.05 parts of n-octylmercaptan and 0.125 parts of t-butyl was added while maintaining the temperature at 80 ° C. The polymerization was completed by standing at 80 ° C. for 2 hours. The obtained polymer latex was salted out, dehydrated, washed with water and dried to obtain a powdery rubber-containing polymer (D-2).

(4) Preparation of Matt Thermoplastic Resin Composition (I):

Copolymers (B), thermoplastic polymers (D-1) and rubber-containing polymers (D-2) prepared by the methods (1), (2) and (3) above and methylmethacryl having a reduced viscosity of 0.051. The thermoplastic polymer (D-3) consisting of the rate / methyl acrylate copolymer (90/10) is mixed in the proportions shown in Table 3 using a Henschel mixer. Each blend is melted, mixed and pelletized in a screw extruder (screw diameter 4 mmφ L / D = 26) at a cylinder temperature of 200 to 260 ° C and a die temperature of 250 ° C. The obtained pellets were dried and molded under the following conditions.

The moldability of the resin, glossiness and appearance of the film were measured and shown in Table 4.

Example 10 to Example 14

The composition of the copolymer (B) and the amounts of the polymers (D-1) to (D-3) were changed as shown in Tables 2 and 3, except that the same results as in Example 9 were obtained. 4 is shown.

Example 15

(1) Preparation of Copolymer (B):

A mixture of the following composition is placed in a reactor equipped with a stirrer, a reflux condenser and a nitrogen gas injector.

The air in the reactor is sufficiently replaced with nitrogen gas, the temperature in the reactor is heated to 75 ° C., and polymerization is carried out while stirring with nitrogen gas. After 3 hours, the temperature in the reactor was raised to 90 ° C. and the temperature was maintained for 45 minutes to complete the polymerization. The reaction product is dehydrated and evaporated to obtain copolymer (B). The obtained beads were 30-500 micrometers in diameter, 100 micrometers in average particle diameter, and particle size distribution is as follows.

(2) Preparation of Matt Thermoplastic Resin Composition (1):

Eight parts of copolymer (B) prepared by the method of (1) above and 100 parts of thermoplastic resin for methacryl film (HIPET HBSOO1, manufactured by Mitsubishi Rayon Co., Ltd., Japan) were melted, extruded and pelletized at 240 ° C. using a twin screw extruder. Make After drying the obtained pellets, a film having a thickness of about 50 mu m is formed by the T-die method. 60 degreeC surface gloss and surface state of the film were measured and shown in Table 5.

Example 16-22

The composition and amount of the copolymer (B) blended with the thermoplastic resin for methacryl film were changed in the same manner as in Example 15 except that shown in Table 5, and the results are shown in Table 5.

Example 23 (Preparation of Laminate)

10 parts of the copolymer (B) prepared by the method (1) of Example 1 and 100 parts of the polymer having the multi-layer structure (C) prepared by the method (2) of Example 1 were blended, and then a twin screw extruder at 240 ° C. Extruded to make pellets. The obtained pellets were dried and molded by co-extrusion with an acrylic resin pellet (ACRYPET VH, manufactured by Mitsubishi Rayon Co., Ltd.) at 240 ° C., and the thickness of the mat thermoplastic resin (I) prepared from the mixture was 100 μm, Table 6 shows the results of measuring the surface gloss and surface condition at 60 ° C. after preparing a thermoplastic resin laminate having excellent mat property of 2 mm thick acrylic resin pellets.

Examples 24-30

The composition and amount of the polymer and the blend copolymer (B) having the multilayer structure (C) were changed as shown in Table 6, respectively, and were the same as in Example 23, and the results are shown in Table 6.

Example 31

The thermoplastic resin in which the mat thermoplastic resin (I) was laminated was changed to polycarbonate resin (LEXAN ^R ML-5500 GE, manufactured by Nippon Plastic Co., Ltd.), and the same procedure as in Example 23 was carried out except that the thermoplastic resin (I) was molded at 280 ° C. Is shown in Table 6.

Example 32

100 parts of polyvinyl chloride resin (P = 720), 3 parts of stabilizer (dibutyl tin maleate), impact modifier (METABLEN ^R C-102, Mitsubishi Rayon Co., Ltd., Japan) ) Changed to a hard polyvinyl chloride resin composition consisting of 10 parts, 1 part of production aid (METABLEN ^R P-551, manufactured by Mitsubishi Rayon Co., Ltd.) and 1 part of lubricant (butyl stearate), and then molded at 200 ° C. Example 23 was carried out and the results are shown in Table 6.

Example 33

The thermoplastic resin in which the mat thermoplastic resin (I) was laminated was changed to ABS resin (DIAPETABS 3001M, manufactured by Mitsubishi Rayon Co., Ltd., Japan), and the same result as in Example 23 was performed except for molding at 240 ° C. Shown in

Example 34

It carried out similarly to Example 23 except having carried out extrusion lamination instead of the coextrusion method. In particular, 10 parts of the copolymer (B) prepared by the method (1) of Example 1 and 100 parts of the polymer having a multi-layer structure (C) were blended and extruded by a twin screw extruder at 240 ° C. to produce pellets. The pellets are dried and a 50 μm thick film is formed by the T-die method. The acrylic resin pellets were extruded at 240 ° C. to prepare a 2 mm sheet, and the formed film was introduced between the molten sheet of the acrylic resin (ACRYPET VH, manufactured by Mitsubishi Rayon Co., Ltd., Japan) and the cooling roll to extrude the laminate. The results are shown in Table 6.

Example 35

It carried out similarly to Example 23 except having heat laminated instead of the coextrusion method. In particular, the film produced by the method of Example 1 (3) using an embossed lamination roll under conditions of 150 ° C. and 30 kg / cm ² was heated and laminated with a soft polyvinyl chloride resin film having a thickness of 100 μm. Was the same as in Example 23, and the results are shown in Table 6.

Example 36 (Preparation of Laminate)

Eight parts of copolymer (B) prepared by the method (1) of Example 15 and 100 parts of thermoplastic resin for methacryl film (HIPET ^R HBSOO1, manufactured by Mitsubishi Rayon Co., Ltd., Japan) were mixed. Extruded to make pellets. The obtained pellets were dried and then molded by coextrusion with acrylic resin pellets (ACRYPET ^R VH, manufactured by Mitsubishi Rayon Co., Ltd., Japan) at 240 ° C. The thickness of the mat thermoplastic resin (I) prepared from the mixture was 100. After preparing a thermoplastic resin laminate having a good mat property having a thickness of 2 mm and an acrylic resin pellet having a thickness of 2 mm, surface gloss and surface state at 60 ° C. were measured, and the results are shown in Table 7.

Examples 37-43

The composition and amount of the polymer and the blend copolymer (B) of the multilayer structure (C) were changed as shown in Table 7, respectively, and were the same as in Example 36, and the results are shown in Table 7.

Example 44

The thermoplastic resin in which the matte thermoplastic resin (I) was laminated was changed to polycarbonate resin (LEXAN ML-5500, manufactured by GE Plastics Corporation of Japan), and the same procedure as in Example 36 was carried out except that the thermoplastic resin was molded at 280 ° C. The results are shown in Table 7.

Example 45

100 parts of polyvinyl chloride resin (P = 720), 3 parts of stabilizer (dibutyltin malate), impact modifier (METABLEN ^R C-102, Mitsubishi Rayon Co., Ltd.) 10 parts, a production aid (METABLEN ^R P-551 manufactured by Mitsubishi Rayon Co., Ltd.) and 1 part of a lubricant (butyl stearate) were changed to hard polyvinyl chloride, and the resultant was molded at 200 ° C. And the results are shown in Table 7.

Example 46

The thermoplastic resin in which the mat thermoplastic resin (I) was laminated was changed to ABS resin (DIAPET ^R ABS3OO1M, manufactured by Mitsubishi Rayon, Japan), and the result was the same as in Example 36 except that it was molded at 240 ° C. Shown in

Example 47

A thermoplastic resin laminate having excellent mat properties was prepared in the same manner as in Example 36 except that the laminate was extruded instead of the coextrusion method. In particular, 8 parts of the copolymer (B) prepared by the method (1) of Example 15 and 100 parts of thermoplastic resin for methacryl film (HIPET ^R HBSOO1, manufactured by Mitsubishi Rayon, Japan) were melted by a twin screw extruder at 240 ° C. It extruded and the pellet was obtained. After drying the obtained pellets, a film having a thickness of about 50 μm was formed by a T-die method, and then an acrylic resin pellet was extruded at 240 ° C. to obtain a sheet of 2 mm, and the formed film was made of acrylic resin (ACRYPET ^R VH, It was introduced between the molten sheet of the Mitsubishi Rayon Co., Ltd. product and the cooling roll, and the extrusion lamination was performed, and the results are shown in Table 7.

Example 48

A thermoplastic resin laminate having excellent mat properties was prepared in the same manner as in Example 36 except that the laminate was heated instead of the coextrusion method. In particular, the film produced by the method of Example 15 (2) using an embossed lamination roll under the conditions of 150 ° C. and 30 kg / cm ² was heated and laminated with a soft polyvinyl chloride resin film having a thickness of 100 μm. Was the same as in Example 36, and the results are shown in Table 7.

Example 49 (Blends with Rigid Polyvinylchloride Resin)

100 parts of polyvinyl chloride resin (P = 720), 3 parts of stabilizer (dibutyltin maleate), 10 parts of impact modifier (METABLEN ^R C-102, manufactured by Mitsubishi Rayon Co., Ltd., Japan), production aid (METABLEN ^R P-551) Copolymer prepared in the same manner as in Example (1), except that 1 part of Mitsubishi Rayon Co., Ltd. product, 1 part of lubricant (butyl stearate), and the composition were changed as shown in Table 8 5 parts) were blended and the blend was mixed on a roll at 165 ° C. followed by 60 ° C. surface gloss. The blend mixed with the roll was pressed at 165 ° C. and 70 tons to prepare a sheet of 2.5 mm, and the Izod impact strength was measured and shown in Table 8.

Example 50 (blend with soft polyvinylchloride resin)

100 parts of polyvinylchloride resin (P = 1100), 50 parts of plasticizer (dioctyl phthalate), 2.5 parts of Cd-Ba type stabilizer, 0.3 parts of stearic acid and 5 parts of copolymer (B) obtained in Example 1 and blended Was mixed in a roll of 155 ℃ and then measured in 60 ℃ surface gloss in a similar manner to Example 49 shown in Table 8.

Examples 51-56

The composition and amount of the copolymer (B) blended with the polyvinyl chloride resin were changed in the same manner as in Example 49 except that the composition and the amount thereof were changed as shown in Table 8, and the results are shown in Table 8.

Example 57 (blend with ABS resin)

5 parts of copolymer (B) prepared in Example 49 and 100 parts of ABS resin (DIAPET ^R ABS3OOl, manufactured by Mitsubishi Rayon Co., Ltd.) were manufactured using a Henschel mixer. Extruded to make pellets. The pellet was dried and injection molded at 200 ° C. to produce a sheet having a thickness of 3 mm, and the Izod impact strength and the surface gloss at 60 ° C. were measured and shown in Table 9 below.

Example 58-Example 63

The composition and amount of the copolymer (B) blended with the ABS resin were the same as in Example 57, except that the composition and amount of the copolymer (B) were changed as shown in Table 9. The measurement results are shown in Table 9.

Example 64 (blend with hard polyvinylchloride resin)

100 parts of polyvinyl chloride resin (P = 720), 3 parts of stabilizer (dibutyl tin maleate), 10 parts of impact modifier (METABLEN ^R C-102, manufactured by Mitsubishi Rayon Co., Ltd., Japan), production aid (METABLEN ^R P-551) 1 part of Mitsubishi Rayon Co., Ltd., 1 part of lubricant (butyl stearate), and 5 parts of copolymer (B) prepared in the same manner as in Example 15 (1), and the blend was rolled at 165 ° C. At 60 ° C surface gloss was measured. The blend mixed with a roll was pressed at a pressure of 70 tons at 165 ° C. to prepare a sheet of 2.5 mm, and the Izod impact strength was measured. The results are shown in Table 10 below.

Example 65 (blend with soft polyvinylchloride resin)

100 parts of polyvinyl chloride resin (P = 1100), 50 parts of plasticizer (dioctylphthalate), 2.5 parts of Cd-Ba type stabilizer, 0.3 parts of stearic acid and 5 parts of copolymer (B) obtained in Example 15 were prepared, The blend was mixed on a roll at 155 ° C. and then 60 ° C. surface gloss was measured in a similar manner to Example 64 and the results are shown in Table 10.

Examples 66-72

The composition and amount of the copolymer (B) blended with the polyvinyl chloride resin were changed in the same manner as in Example 64 except for changing as shown in Table 10, and the results are shown in Table 10.

Example 73 (Blends with ABS Resin)

5 parts of copolymer (B) prepared by the method of Example 15 (1) in a Henschel mixer and 100 parts of ABS resin (DIAPET ^R ABS3OOl, manufactured by Mitsubishi Rayon Co., Ltd., Japan), and a screw having a diameter of 400 mmφ at 230 ° C. Extruded with extruder to make pellets. The pellet was dried and injection molded at 200 ° C. to produce a sheet having a thickness of 3 mm, and then measured by Izod impact strength and surface gloss at 60 ° C., and the results are shown in Table 11.

Examples 74-80

The composition and amount of the copolymer (B) blended with the ABS resin were changed in the same manner as in Example 73, except that the composition and amount thereof were changed as shown in Table 11, and the results are shown in Table 11.

Comparative Example 1

A film having a thickness of 50 μm was formed by the same method as in Example 1 (3) using only the polymer having a multilayer structure (C) prepared by the method (2) of Example 1, and the surface glossiness and surface state of the film were measured at 60 ° C. The measurement is shown in Table 1. Here, it can be seen that the mat properties do not improve when the copolymer (B) is not used.

Comparative Example 2

100 parts of a polymer having a multilayer structure (C) prepared by the method of Example 1 (2) and 10 parts of a crosslinking mat agent (METABLEN ^R F410, manufactured by Mitsubishi Rayon Co., Ltd., Japan) were prepared. After molding a film having a thickness of 50㎛ in the same manner as in the following, 60 ℃ clear gloss and surface state of the film was measured and shown in Table 1. It can be seen that, by polymerizing the (meth) acrylic acid hydroxyalkyl ester, the mat property can be improved without damaging the surface state.

Comparative Example 3-Comparative Example 5

As shown in Table 1, except that the composition of the copolymer (B) was changed, it was carried out in the same manner as in Example 1, and the results are shown in Table 1. It can be seen that the composition of the copolymer (B) is important for obtaining a resin composition having excellent mat properties here.

Comparative Example 6

The same procedure as in Example 9 was carried out except that the crosslinking mat agent (METABLEN ^R F410, manufactured by Mitsubishi Rayon, Japan) was used instead of the copolymer (B). The results are shown in Table 4. It was found that the copolymer (B) can improve the mat property.

Comparative Example 7

Except not using the copolymer (B), and was carried out in the same manner as in Example 9, the results are shown in Table 4. It was found that the mat property did not improve when the copolymer (B) was not used.

Comparative Example 8

Except not using the thermoplastic polymer (D-1), and was carried out in the same manner as in Example 9, the results are shown in Table 4. Here, it can be seen that a film having excellent properties cannot be produced when the thermoplastic polymer (D-1) is not used.

Comparative Example 9

The same procedure as in Example 9 was carried out except that the amount of the (meth) acrylic acid hydroxyalkyl ester in the copolymer (B) was increased to 85 parts. The results are shown in Table 4.

If the amount of the (meth) acrylic acid hydroxyalkyl ester in the copolymer (B) exceeds 85 parts, it can be seen that a film having excellent properties cannot be produced.

Comparative Example 10

Except not using the rubber-containing polymer (D-2) and in the same manner as in Example 9 and the results are shown in Table 4. It was found that the mat properties did not improve when the rubber-containing polymer (D-2) was not used.

Comparative Example 11

The mixture of the following composition was put in the reactor, and it carried out similarly to Example 15, and the result is shown in Table 5.

Here, it was found that by using the copolymer containing the (meth) acrylic acid hydroxyalkyl ester unit, the mat property can be improved without damaging the surface state.

Comparative Example 12

Using a thermoplastic resin for methacryl film (HIPET ^R HBSOO1, manufactured by Mitsubishi Rayon Co., Ltd., Japan), a 50 μm thick film was formed in the same manner as in Example 15 (2). The measurement is shown in Table 5.

Comparative Example 13

The composition and amount of the copolymer (B) blended with the thermoplastic resin for methacryl film were changed as shown in Table 5, except that the composition was the same as in Example 15, and the results are shown in Table 5. It was found that the composition of the copolymer (B) related to the combination of the non-crosslinkable monomer and the amount of the crosslinkable monomer is important in order to obtain an excellent matt thermoplastic resin composition.

Comparative Example 14

The film was formed using only a polymer having a multilayer structure (C) prepared by the method of Example 1 (2), and laminated in the same manner as in Example 23, and then the surface glossiness and surface state of the laminate were measured. Shown in

Comparative Example 15

100 parts of the polymer having a multilayer structure (C) prepared in the method of Example 1 (2) and 10 parts of a crosslinking mat agent (METABLEN ^R F410, manufactured by Mitsubishi Rayon Co., Ltd., Japan) were blended in the same manner as in Example 23. The lamination was performed, and the surface gloss and surface state of the laminate were measured and shown in Table 6.

Comparative Example 16 to Comparative Example 18

As shown in Table 6, except that the composition of the copolymer (B) was changed, the same procedure as in Example 23 was carried out to prepare a laminate, and the surface gloss and surface state of the laminate were measured and shown in Table 6. .

Comparative Example 19

A laminate was prepared in the same manner as in Example 36, except that the composition of the copolymer (B) was changed as shown in Table 7. The surface gloss and surface state of the laminate were measured and shown in Table 7. It was.

Comparative Example 20

A laminate was prepared in the same manner as in Example 36 except that the copolymer (B) was not used, and the surface gloss and surface state of the laminate were measured and shown in Table 7.

Comparative Example 21

A laminate was prepared in the same manner as in Example 36, except that the composition of the copolymer (B) was changed as shown in Table 7. The surface gloss and surface state of the laminate were measured and shown in Table 7. It was.

Comparative Example 22

Except for using the silica gel instead of the copolymer (B) was carried out in the same manner as in Example 49, and the results are shown in Table 8.

Comparative Example 23

Except for using the silica gel instead of the copolymer (B) was carried out in the same manner as in Example 50, and the results are shown in Table 8.

Comparative Example 24

As shown in Table 8, except that the composition of the copolymer (B) was changed, it was the same as in Example 49, and the results were measured and shown in Table 8.

Comparative Example 25

As shown in Table 8, except that the composition of the copolymer (B) was changed, it was the same as in Example 50, and the results were measured and shown in Table 8.

Comparative Example 26

Except that the copolymer (B) was not used, it was the same as in Example 49, and the results are shown in Table 8.

Comparative Example 27

Except that the copolymer (B) was not used, it was the same as in Example 50, and the results are shown in Table 8.

Comparative Examples 28-29

The composition and amount of the copolymer (B) blended with the polyvinyl chloride resin were the same as in Example 49, except that the composition and amount were changed as shown in Table 8. The results are measured and shown in Table 8.

Comparative Example 30

Except for blending the silica gel instead of the copolymer (B) and in the same manner as in Example 57, the results were measured and shown in Table 9.

Comparative Example 31

As shown in Table 9, except that the composition of the copolymer (B) was changed, it was the same as in Example 57, and the results were measured and shown in Table 9.

Comparative Example 32

Except that the copolymer (B) was not used, it was the same as in Example 57, and the results are shown in Table 9.

Comparative Example 33

The composition and amount of the copolymer (B) blended with the ABS resin were the same as in Example 57, except that the composition and amount of the copolymer (B) were changed as shown in Table 9. The results are measured and shown in Table 9.

Comparative Example 34

Except for using the silica gel instead of the copolymer (B) was the same as in Example 64, and the results are shown in Table 10.

Comparative Example 35

Except for using the silica gel instead of the copolymer (B) was the same as in Example 65 and the results are shown in Table 10.

Comparative Example 36

Except that the copolymer (B) prepared in Comparative Example 11 was used in the same manner as in Example 64, and the results are shown in Table 10.

Comparative Example 37

Except for using the copolymer (B) prepared in Comparative Example 11 and was carried out in the same manner as in Example 65, the results were measured and shown in Table 10.

Comparative Example 38

Except that the copolymer (B) was not used, it was the same as in Example 64, and the results are shown in Table 10.

Comparative Example 39

Except that the copolymer (B) was not used, it was the same as in Example 65, and the results are shown in Table 10.

Comparative Example 40

As shown in Table 10, except that the composition of the copolymer (B) was changed, it was the same as in Example 64, and the results were measured and shown in Table 10.

Comparative Example 41

Except having used the copolymer (B) prepared in Comparative Example 11 it was the same as in Example 73, and the results are shown in Table 11.

Comparative Example 42

Except that the copolymer (B) was not used, it was the same as in Example 73, and the results are shown in Table 11.

Comparative Example 43

As shown in Table 11, except that the composition of the copolymer (B) was changed, it was the same as in Example 73, and the results were measured and shown in Table 11.

Claims (28)

0.5-80 weight% of (meth) acrylic-acid hydroxy alkyl esters (b-1) of a C1-C8 alkyl group of an alkyl group, and methacrylic acid alkyl ester of C1-C13 of an alkyl group (b) with respect to 100 weight part of thermoplastic resins (A) -2) 10-99% by weight, 0-79% by weight of acrylic acid alkyl ester (b-3) having 1 to 8 carbon atoms of alkyl group, 0-70% by weight of vinyl aromatic monomer (b-4) and monoethylenically unsaturated monomer ( b-5) 100% by weight of the non-crosslinkable monomer mixture (B-1) consisting of 0-20% by weight and 0-5% by weight of copolymerizable crosslinkable monomer (B-2) having two or more double bonds in the molecule A thermoplastic resin composition having excellent mat properties, wherein the mixture is blended with 0.1-40 parts by weight of a copolymer (B) obtained by suspension polymerization. The thermoplastic resin composition according to claim 1, wherein the copolymer (B) is prepared without using a copolymerizable crosslinkable monomer (B-2) having two or more double bonds in a molecule. The thermoplastic resin composition according to claim 1, wherein the copolymer (B) is prepared using 5 parts by weight or less of the crosslinkable monomer (B-2) based on 100 parts by weight of the non-crosslinkable monomer mixture (B-1). . The thermoplastic resin composition according to claim 1, wherein the copolymer (B) is prepared by suspension polymerization. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is an acrylic resin. The acrylic resin (A) is 80-100% by weight of an acrylic acid alkyl ester having 1 to 8 carbon atoms or a methacrylic acid alkyl ester having 1 to 4 alkyl groups (C-al). 0-20% by weight of copolymerizable monomer (C-a2) having two double bonds, 0-10% by weight of multifunctional monomer (C-a3), graft binder of (C-al)-(C-a3) 80-100% by weight of the innermost polymer (Ca) prepared from a mixture composed of 0.1-5 parts by weight of the total amount and the acrylic acid alkyl ester having 1 to 8 carbon atoms (C-b1) 0-20% by weight of the copolymerizable monomer (C-b2) having a double bond, 0-10% by weight of the multifunctional monomer (C-b3) and the total amount of the (C-b1)-(C-b3) component of the graft binder Alkyl methacrylate having 1 to 4 carbon atoms and a crosslinked elastomer (Cb) prepared from a mixture composed of 0.1 to 5 parts by weight based on 100 parts by weight Outermost polymer having a glass transition temperature of 60 ° C. or higher prepared from a mixture of (C-cl) of 51-100% by weight and a copolymerizable monomer (C-c2) having one double bond (C-c2) of 0-49% by weight ( Methacrylic acid alkyl ester (C-d2) having 10-90% by weight of acrylic acid alkyl ester (C-dl) having an alkyl group having 1 to 8 carbon atoms and an alkyl group having 1 to 4 carbon atoms 10-90% by weight, 0-20% by weight of copolymerizable monomer (C-d3) with double bond, 0-10% by weight of multifunctional monomer (C-d4), graft crosslinker (C-d1)-(C -d2) at least one intermediate layer (Cd) prepared from a mixture consisting of 0.1-5 parts by weight with respect to 100 parts by weight of the total amount of monomers, wherein the amount of alkyl acrylate ester in the polymer is It has a multilayer structure (C) which is reduced toward the outer layer polymer (Cc), the gel content is 50% or more, and the amount of residual metal is less than 500 ppm. The thermoplastic resin composition characterized in that the methacrylic or methacrylic polymer. The acrylic resin (A) is 0.1-20% by weight of the thermoplastic resin (D-1), rubber-containing polymer (D) based on 100% by weight of the total amount of the polymer (D-1) -polymer (D-3). -2) acrylic polymer (D) consisting of 5-80% by weight and 0-93.9% by weight of thermoplastic polymer (D-3), wherein thermoplastic polymer (D-1) comprises 50-100% by weight of methyl methacrylate and at least 1 It is made from 0-50% by weight of two other copolymerizable vinyl monomers, and has a reducing viscosity of 0.1 L / g or more (measured by dissolving 0.1 g of polymer in 100 ml of chloroform at 25 ° C) and a rubber-containing polymer (D-2 ) Is an elastomer obtained by polymerizing 10-2000 parts by weight of one monomer or polymerizing a mixture composed of 50-99.9% by weight of an alkyl acrylate ester, 0-40% by weight of a copolymerizable vinyl monomer and 0.1-10% by weight of a copolymerizable crosslinkable monomer. Vinyl monomer copolymerizable with 50-100 parts by weight of methacrylic acid ester in the presence of 100 parts by weight of copolymer It is prepared by polymerizing 10-2000 parts by weight of a monomer mixture composed of 0-50% by weight, and the thermoplastic polymer (D-3) is 50-99.9% by weight of methacrylic acid ester having 1-4 alkyl groups and 1-8 carbon atoms. 0.1-50% by weight of an acrylic acid ester having 2 alkyl groups and 0-50% by weight of one or more vinyl monomers capable of copolymerization therewith, and 0.1g / g of polymer in a reduced viscosity of less than 0.1 L / g (25 ° C., 100 ml of chloroform). Dissolved and measured), characterized in that the thermoplastic resin composition. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyvinyl chloride resin. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is an ABS resin. 6. The thermoplastic resin composition according to claim 5, wherein the haze is 10% or less. 0.5-80% by weight of (meth) acrylic acid hydroxy alkyl ester (b-1) having 1 to 8 carbon atoms of an alkyl group, and 1 to 13 carbon atoms of an alkyl group, based on 100 parts by weight of the thermoplastic base resin (E) or the thermoplastic resin (A). 10-99 weight% of methacrylic acid alkyl esters (b-2), 0-79 weight% of acrylic acid alkyl esters (b-3) having 1 to 8 carbon atoms of an alkyl group, and 0-70 weight% of vinyl aromatic monomers (b-4) And a copolymerizable crosslinkable monomer (B-2) having 100% by weight of a non-crosslinkable monomer mixture (B-1) comprising 0-20% by weight of a monoethylenically unsaturated monomer (b-5) and two or more double bonds in a molecule thereof. A thermoplastic resin laminate composed of a thermoplastic resin composition characterized by blending a copolymer (B) obtained by suspension polymerization in an amount of 0-5% by weight with 0.1-40 parts by weight. The thermoplastic resin laminate according to claim 11, wherein the copolymer (B) is prepared without using a copolymerizable crosslinkable monomer (B-2) having two or more double bonds in a molecule. The thermoplastic resin laminate according to claim 11, wherein the copolymer (B) is prepared using 5 parts by weight or less of a crosslinkable monomer (B-2). The thermoplastic resin laminate according to claim 11, wherein the copolymer (B) is prepared by suspension polymerization. The thermoplastic resin laminate according to claim 11, wherein the thermoplastic resin (A) is acrylic or methacrylic resin. The thermoplastic resin laminate according to claim 15, wherein the thermoplastic resin (A) is an acrylic or methacrylic resin having a multilayer structure (C) as defined in claim 6. 16. The thermoplastic resin laminate of claim 15, wherein the thermoplastic resin (A) is an acrylic or methacryl polymer (D) as defined in claim 7. The thermoplastic resin laminate according to claim 11, wherein the thermoplastic resin (A) is a polyvinyl chloride resin. The thermoplastic resin laminate according to claim 11, wherein the thermoplastic resin (A) is an ABS resin. The thermoplastic resin laminate according to claim 11, wherein the thermoplastic base resin (E) is an acrylic resin. The thermoplastic resin laminate according to claim 11, wherein the thermoplastic base resin (E) is a polycarbonate resin. The thermoplastic resin laminate according to claim 11, wherein the thermoplastic base resin (E) is a polyvinyl chloride resin. The thermoplastic resin laminate according to claim 11, wherein the thermoplastic base resin (E) is an ABS resin. The thermoplastic resin laminate according to claim 11, wherein the thermoplastic resin laminate is manufactured by coextrusion. The thermoplastic resin laminate according to claim 11, wherein the thermoplastic resin laminate is prepared by extrusion lamination. The thermoplastic resin laminate according to claim 11, wherein the thermoplastic resin laminate is prepared by a heat lamination method. 0.5-80 weight% of (meth) acrylic-acid hydroxy alkyl ester (b-1) of C1-C8 alkyl of an alkyl group, 10-99 weight% of methacrylic acid alkyl ester (b-2) of C1-C13 of an alkyl group, an alkyl group 0-79% by weight of acrylic acid alkyl ester (b-3) having 1 to 8 carbon atoms, 0-70% by weight of vinyl aromatic monomer (b-4) and 0-20% by weight of monoethylenically unsaturated monomer (b-5) 0-5 parts by weight of a non-crosslinkable monomer mixture (B-1) and a copolymerizable crosslinkable monomer (B-2) having two or more double bonds in a molecule are made based on 100 parts by weight of the monomer mixture (B-1). It is an obtained copolymer (B), The thermoplastic resin mat agent characterized by the above-mentioned. 0.5-80 weight% of (meth) acrylic-acid hydroxy alkyl esters (b-1) of a C1-C8 alkyl group of an alkyl group, and methacrylic acid alkyl ester of C1-C13 of an alkyl group (b) with respect to 100 weight part of thermoplastic resins (A) -2) 10-99% by weight, alkyl ester of acrylic acid (b-3) 0-79% by weight of alkyl group, 0-70% by weight of vinyl aromatic monomer (b-4) and monoethylenically unsaturated monomer ( b-5) 100 weight of the non-crosslinkable monomer mixture (B-1) which consists of 0-20 weight%, and the copolymerizable crosslinkable monomer (B-2) which has 2 or more double bonds in a molecule | numerator 0.1-40 parts by weight of a copolymer (B) obtained by polymerizing 0-5 parts by weight with respect to a part, wherein the mat method of the thermoplastic resin (A).