JPH09272777A - Thermoplastic resin composition and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable a film with a good matte finish to be obtd. irrespective of molding conditions by compounding an acrylic resin with a hydroxylated linear polymer. SOLUTION: 1-80wt.% hydroxyalkyl (meth)acrylate having a 1-8C hydroxyalkyl group, 10-99wt.% alkyl methacrylate having a 1-13C alkyl group, 0-79wt.% alkyl acrylate having a 1-8C alkyl group, and 0-50wt.% other copolymerizable monomer are copolymerized to give a hydroxylated linear polymer having an intrinsic viscosity (25 deg.C, in chloroform) of 0.03-0.3l/g. A matte thermoplastic resin compsn. is obtd. by compounding 100 pts.wt. acrylic resin with 1-40 pts.wt. above-obtd. linear polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition that exhibits good matting properties regardless of shaping conditions, and a laminate using the same.

[0002]

2. Description of the Related Art Molded articles of thermoplastic resins such as acrylic resins are generally glossy, which is an important characteristic for some applications. However, on the other hand, there are many applications that do not require such luster or are preferred to have no luster. The matte appearance is particularly preferred for applications such as vehicle interior materials, furniture and housings for electric devices, wallpaper, and building materials.

[0003] The conventional matting methods for thermoplastic resins are roughly classified into (1) a method by imprinting and matting, and (2)
The method is divided into a method of adding an inorganic or organic matting agent.

The above method (1) generally has the advantage of less deterioration of physical properties, but has poor productivity and high processing cost, and the matting effect is insufficient. In many cases, secondary processing is performed. Not suitable for use. On the other hand, the above (2)
The method of (1) can control the degree of matting without significantly lowering the productivity, and can be applied to the application of secondary processing, but it has a serious problem of deterioration of physical properties. Particularly when an inorganic material such as silica gel is used as a matting agent, the physical properties such as impact resistance, strength and elongation, and transparency are remarkably deteriorated.

As a method of using an organic substance, especially a high-molecular matting agent, cross-linking having an average particle diameter of 35 to 500 μ obtained by suspension polymerization as described in JP-A-56-36535. There is a method using a polymer. In this method, physical properties such as impact resistance and strength and elongation are not significantly deteriorated, but the matting effect is insufficient. In addition, since the polymer used in this method is a polymer having a semi-crosslinked structure, when it is formed into a film, it is relatively easy to cause lumps. Further, when it is used as an acrylic resin to form a film, it has a problem that it cannot be used in applications requiring transparency because of its poor transparency.

[0006] Further, a method using a polymeric matting agent is proposed in European Patent EP-627469. In this way, the mattness, appearance and transparency are greatly improved.

[0007]

However, the matte film obtained by the above method (2) has a problem that the matteness greatly changes depending on the shaping conditions.

The present invention is intended to solve this problem, and relates to a thermoplastic resin composition which constantly exhibits good mattness under different shaping conditions.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that acrylic acid hydroxyalkyl ester and / or methacrylic acid hydroxyalkyl ester having a specific intrinsic viscosity are contained. The present invention has been found out that by blending the linear polymer (B) described above with an acrylic resin, a good matting property is constantly exhibited even under different shaping conditions.

That is to say, the gist of the present invention is that a matting agent is obtained by adding 1 to 40 parts by weight of a linear polymer (B) having a hydroxyl group shown below to 100 parts by weight of an acrylic resin (A). Thermoplastic resin composition (I) and a laminate having the thermoplastic resin composition (I) in at least the surface layer.

(B) Linear Polymer Having Hydroxyl Group Acrylic hydroxyalkyl ester having 1 to 8 carbon atoms of alkyl group and / or methacrylic acid hydroxyalkyl ester (b-1) 1 to 80% by weight, alkyl group 10 to 99% by weight of a methacrylic acid alkyl ester (b-2) having 1 to 13 carbon atoms, and an alkyl group having a carbon number of 1 to 1
Obtained by polymerizing 0 to 79% by weight of an alkyl acrylate (b-3) of 8 and at least 0 to 50% by weight (b-4) of another copolymerizable vinyl monomer. Yes, and intrinsic viscosity (using chloroform as the solvent, 2
A linear polymer having a hydroxyl group in the range of 0.05 to 0.3 L / g (measured at 5 ° C.).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION As the acrylic resin (A) used in the present invention, known ones can be used. The acrylic resin referred to herein means a resin composition containing 20% by weight or more of a methacrylic acid alkyl ester and / or an acrylic acid alkyl ester. Among the acrylic resins, the multilayer structure polymer (A-
1) Alternatively, the polymer (A-2) is particularly excellent in moldability and matte expression.

The multi-layer structure polymer (A-
1) is (i) an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms or a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms (A-1-a).
1) 80 to 100 parts by weight, 0 to 20 parts by weight of another monomer (A-1-a2) having a copolymerizable double bond, and 0 to polyfunctional monomer (A-1-a3). The innermost layer polymer (A-1-a) obtained by polymerizing 0.1 to 5 parts by weight of the graft crossing agent (A-1-a4) per 100 parts by weight of the total amount of 10 parts by weight, (ii). ) Acrylic acid alkyl ester (A-1-b1) 80 having an alkyl group having 1 to 8 carbon atoms
To 100 parts by weight, 0 to 20 parts by weight of another monomer (A-1-b2) having a copolymerizable double bond, and 0 to 10 parts by weight of a polyfunctional monomer (A-1-b3). Of the graft crossing agent (A-1-
b4) is polymerized to obtain a crosslinked elastic polymer (A-1-
b), (iii) 51 to 100 parts by weight of a methacrylic acid alkyl ester (A-1-c1) having 1 to 4 carbon atoms, and another monomer (A-1-c) having a copolymerizable double bond.
2) The outermost layer polymer (A-1-c) having a glass transition temperature of 60 ° C. or higher obtained by polymerizing 0 to 49 parts by weight is used as a basic structure, and the crosslinked elastic polymer (A-1-b) is used. And (iv) the outermost layer polymer (A-1-c) has 1 to 8 carbon atoms.
Acrylic acid alkyl ester (A
-1-d1) 10 to 90% by weight, methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms (A-1-
d2) 10 to 90% by weight, 0 to 20 parts by weight of a monomer (A-1-d3) having a copolymerizable double bond, and a polyfunctional monomer (A-1-d4) 0 to 10 Total amount by weight 1
The amount of the alkyl acrylate obtained by polymerizing 0.1 to 5 parts by weight of the graft crossing agent (A-1-d5) with respect to 00 parts by weight is from the above crosslinked elastic polymer (A-1-b). At least one intermediate layer polymer (A-1-) that monotonically decreases toward the outermost layer polymer (A-1-c).
It has a layer of d) and has a gel content of 50% by weight or more.

In the present invention, the multilayer structure polymer (A-
The acrylic acid alkyl ester or methacrylic acid alkyl ester (A-1-a1) used for constituting the innermost layer polymer (A-1-a) of 1) has 1 carbon atoms.
Alkyl acrylate having an alkyl group of 8 to 8 such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, etc., and alkyl having 1 to 4 carbon atoms. Examples of the alkyl methacrylate having a group, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, are used. As the acrylic acid alkyl ester, one having a low glass transition temperature (hereinafter abbreviated as Tg) is used. Is preferred. These acrylic acid alkyl esters and methacrylic acid alkyl esters are used singly or as a mixture of two or more kinds, and the amount thereof is the monomer (A-1-a
80) in 100 parts by weight of the total amount of 1) to (A-1-a3).
It is used in the range of １００100 parts by weight. Further, it is most preferable to use these acrylic acid alkyl esters or methacrylic acid alkyl esters in a unified manner in the polymer of each stage to be subsequently polymerized, but depending on the final purpose, two or more kinds of monomers may be used. They can be used as a mixture, or different kinds of acrylic acid alkyl ester or methacrylic acid alkyl ester can be used.

Other monomers (A-1-a2) having a double bond capable of copolymerization include higher alkyl esters of acrylic acid, lower alkoxy esters of acrylic acid, cyanoethyl esters of acrylic acid, acrylamide, acrylic acid and methacrylic acid. It is preferable to use an acrylic monomer such as an acid, and it is used in the range of 0 to 20 parts by weight in 100 parts by weight of the total amount of the monomers (A-1-a1) to (A-1-a3). As the other monomer, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, etc. can be used in the component (A-1-a) within a range not exceeding 20 parts by weight. These monomers are used alone or in combination of two or more.

Examples of the polyfunctional monomer (A-1-a3) include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and dimethacrylate 1,4.
-The use of butylene glycol and alkylene glycol dimethacrylate such as propylene glycol methacrylate is preferred, and polyvinylbenzene such as divinylbenzene and trivinylbenzene, and alkylene glycol diacrylate can also be used.
These monomers work effectively for bridging the layers in which they are contained, and do not act for bonding between layers with other layers. The polyfunctional monomer (A-1-a3) gives a fairly stable multilayer structure as long as the graft crossing agent is present even if it is not used at all, but when the hot strength is strictly required, It is optionally used depending on the purpose of addition. The amount used is 0 to 10 parts by weight in 100 parts by weight of the total amount of the monomers (A-1-a1) to (A-1-a3). If the amount used exceeds 10 parts by weight, the physical properties of the multilayer structure polymer will be deteriorated.

As the graft crossing agent (A-1-a4), an allyl, methallyl or crotyl ester of a copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid, preferably acrylic acid, methacrylic acid, maleic acid and Examples include allyl esters of fumaric acid. Especially, allyl methacrylate has an excellent effect. In addition, triallyl cyanurate and triallyl isocyanurate are also effective. In such a graft crossing agent, mainly the conjugated unsaturated bond of the ester reacts much faster than the allyl group, the methallyl group or the crotyl group, and chemically bonds. During this time, substantially all part of the allyl group, methallyl group or crotyl group is effective during the polymerization of the polymer for the next layer to give a graft bond between two adjacent layers.

The amount of the graft crossing agent used is extremely important, and is 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the monomers (A-1-a1) to (A-1-a3). It is preferably used in the range of 0.5 to 2 parts by weight. If it is less than 0.1 part by weight, the effective amount of graft bond is small, and if it exceeds 5 parts by weight, the reaction amount with the crosslinked elastic polymer (A-1-b) polymerized and formed in the next second stage. Is large, which is one of the features of the present invention. The two-layer crosslinked rubber elastic body has the two-layer elastic body structure (the innermost layer polymer (Aa) has a crosslinked elastic body (A
(1-b) layer is formed), resulting in lower elasticity.

The content of the innermost layer polymer (A-1-a) in the multilayer structure polymer (A-1) is preferably in the range of 5 to 35% by weight, more preferably 5 to 15% by weight, and crosslinked. It is preferably lower than the content of the elastic polymer (A-1-b).

Next, the crosslinked elastic polymer (A-1-b) constituting the multilayer structure polymer (A-1) is an important component for imparting rubber elasticity to the multilayer structure polymer (A-1). is there.

Alkyl acrylates (A-1-) used for constituting the crosslinked elastic polymer (A-1-b)
As b1), the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms described in (A-1-a1) of the innermost layer polymer (A-1-a) is used. The amount of the acrylic acid alkyl ester (A-1-b1) used is in the range of 80 to 100 parts by weight in 100 parts by weight of the total amount of the monomers (A-1-b1) to (A-1-b3). is there.
In particular, since the crosslinked elastic polymer (A-1-b) is an elastic body, it preferably has a low Tg, and the main component alkyl acrylate (A-1-b1) is n-butyl acrylate. Use is preferred.

As the other monomer (A-1-b2) having a copolymerizable double bond, the above innermost layer polymer (A-1) is used.
-A) a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms described in (A-1-a1),
The monomer described in (A-1-a2) is used. Other monomer having copolymerizable double bond (A-1-b2)
The amount of the monomer used is from (A-1-b1) to (A-1-b1).
It is in the range of 0 to 20 parts by weight in the total amount of 100 parts by weight of 3). If the amount used exceeds 20 parts by weight, rubber elasticity will be deteriorated.

As the polyfunctional monomer (A-1-b3), (A-1-a) of the above innermost layer polymer (A-1-a) is used.
The monomers described in 3) are used. The amount of the polyfunctional monomer (A-1-b3) used is the monomer (A-1-b1).
To (A-1-b3) in a total amount of 100 parts by weight, 0 to 10
It is in the range of parts by weight. If the amount used exceeds 10 parts by weight, the physical properties of the multi-layer structure polymer will be deteriorated.

The graft crossing agent (A-1-b4) is (A-1-a) of the innermost layer polymer (A-1-a).
The compounds described in 4) are used. The amount of the graft crossing agent (A-1-b4) used is the monomer (A-1-b1).
.About. (A-1-b3) in an amount of 0.
It is in the range of 1 to 5 parts by weight.

The content of the crosslinked elastic polymer (A-1-b) in the multilayer structure polymer (A-1) is preferably in the range of 10 to 45% by weight, and the content of the innermost layer polymer (A-1-a) is More preferably, it is higher than the content.

A two-layer crosslinked rubber elastic body comprising the innermost layer polymer (A-1-a) and the crosslinked elastic polymer (A-1-b) has a gel content determined by the following measuring method. In order to obtain excellent solvent resistance and hot water whitening resistance, it is preferable that the content is 85% by weight or more and the degree of swelling is set in the range of 3 to 13.

Method for measuring gel content and swelling degree According to JIS K-6388, a predetermined amount of a two-layer crosslinked rubber elastic polymer was sampled and penetrated into methyl ethyl ketone (hereinafter abbreviated as MEK) at 25 ° C. for 48 hours. After swelling, it was pulled up, the attached MEK was wiped off, the weight thereof was measured, and then the MEK was removed in a vacuum dryer to measure the absolute dry weight, which was calculated by the following formula.

Swelling degree = (weight after MEK swelling−excess dry weight) / excess dry weight Gel content (%) = (excess dry weight / weight of collected sample) ×
100 Furthermore, the outermost layer polymer (A-1-c) that constitutes the multilayer structure polymer (A-1) is a component that imparts moldability and mechanical properties to the multilayer structure polymer (A-1). .

The methacrylic acid alkyl ester (A-1-) used for constituting the outermost layer polymer (A-1-c).
As c1), the methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms described in (A-1-a1) of the innermost layer polymer (A-1-a) is used, but the appearance is The use of methyl methacrylate is preferred. The amount of the methacrylic acid alkyl ester used is in the range of 51 to 100 parts by weight (total 100 parts by weight) in 100 parts by weight of the total amount of the monomers (A-1-c1) to (A-1-c2). . If the amount used is less than 51 parts by weight, Tg will be low, and the physical properties will be deteriorated as described below.

As the other monomer (A-1-c2) having a double bond capable of copolymerization, the above innermost layer polymer (A-1) is used.
-A) an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms described in (A-1-a1),
The monomer described in (A-1-a2) is used. Other monomer having copolymerizable double bond (A-1-c2)
The amount of the monomer used is from (A-1-c1) to (A-1-c1).
It is in the range of 0 to 49 parts by weight in the total amount of 100 parts by weight of 2). When the amount used exceeds 49 parts by weight, Tg becomes low,
The physical properties will be deteriorated as described below.

The outermost layer polymer (A-1-c) is composed of the above-mentioned monomers (A-1-c1) and (A-1-c2), but has excellent solvent resistance and hot water resistance. In order to obtain the whitening property, it is necessary that the outermost layer polymer (A-1-c) has a Tg of 60 ° C. or higher, preferably 80 ° C. or higher. Outermost layer polymer (A-1-c) alone has Tg of 60.
When the temperature is lower than 0 ° C, even if the gel content of the multi-layer structure polymer (A-1) is 50% by weight or more, it becomes difficult to obtain a polymer having excellent solvent resistance and hot water whitening resistance.

The content of the outermost layer polymer (A-1-c) in the multilayer structure elastic polymer (A-1) is 10 to 80% by weight.
Is preferable, and more preferably 40 to 60% by weight.

The multilayer structure polymer (A-1) of the present invention includes the above innermost layer polymer (A-1-a) and the crosslinked elastic polymer (A-1).
-B) and the outermost layer polymer (A-1-c) as a basic structure, and further between the innermost layer polymer (A-1-b) and the outermost layer polymer (A-1-c). , Intermediate layer polymer (A-1-
The layer of d) is provided.

The intermediate layer polymer (A-1-d) has a carbon number of 1
Acrylic acid alkyl ester having 1 to 8 alkyl groups (A-1-d1), methacrylic acid alkyl ester having 1 to 4 carbon alkyl groups (A-1-d2), having a double bond capable of copolymerization It is composed of a monomer (A-1-d3), a polyfunctional monomer (A-1-d4), and a graft crossing agent (A-1-d5). Intermediate layer polymer (A-
1-d) is a layer that connects the crosslinked elastic polymer (A-1-b) layer and the outermost polymer (A-1-c) layer, and affects the whitening property in hot water, and thus the intermediate layer polymer. The amount of the alkyl acrylate (A-1-d1) constituting (A-1-d) is from the crosslinked elastic polymer (A-1-b) to the outermost layer polymer (A
At least 1 so as to decrease monotonically toward (1-c).
It is necessary that two layers be provided.

Acrylic acid alkyl ester (A-1-d) used for constituting the intermediate layer polymer (A-1-d).
1) is (A) of the innermost layer polymer (A-1-a).
-1-a1) and the crosslinked elastic polymer (A-1-b)
The acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms described in (A-1-b1) of is used. The amount used is from monomers (A-1-d1) to (A-1-
It is in the range of 10 to 90 parts by weight in the total amount of 100 parts by weight of d4).

Methacrylic acid alkyl ester (A-1-
As d2), (A-1-a1) of the innermost layer polymer (A-1-a) and the outermost layer polymer (A-1-
The methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms described in (A-1-c1) of c) is used. The amount used is from (A-1-d1) to (A
The total amount of -1-d4) is in the range of 10 to 90 parts by weight in 100 parts by weight.

A monomer having a double bond capable of copolymerization (A
-1-d3) and the polyfunctional monomer (A-1-d4) include (A-1-a) of the innermost layer polymer (A-1-a).
The monomers described in 2) and (A-1-a3) can be used. The amount of each used monomer (A-1
-D1) to (A-1-d4) in 100 parts by weight in total,
It is in the range of 0 to 20 parts by weight and 0 to 10 parts by weight.

Examples of the graft crossing agent (A-1-d5) include (A-1-a) of the above innermost layer polymer (A-1-a).
The compounds described in 4) are used. The amount used is 100 in total of the monomers (A-1-d1) to (A-1-d4).
It is in the range of 0.1 to 5 parts by weight with respect to parts by weight. The graft crossing agent (A-1-d5) used in the intermediate layer polymer (A-1-d) is a crosslinked elastic polymer (A-1-b).
It is an essential component for closely bonding the outermost layer polymer (A-1-c) and obtaining excellent properties.

The content of the intermediate layer polymer (A-1-d) in the multilayer structure polymer (A-1) is preferably in the range of 5 to 35% by weight, more preferably 7 to 25% by weight. 5
When the content is less than 5% by weight, the function as an intermediate layer is lost, while
If it exceeds 5% by weight, the balance of the multilayer structure polymer will be impaired.

The multilayer structure polymer (A-
1) is the innermost layer polymer (A-1-a), the crosslinked elastic polymer (A-1-b), the outermost layer polymer (A-1-c),
And a polymer layer of the intermediate layer polymer (A-1-d). In order to exhibit excellent matting properties in the acrylic film of the present invention, the multilayer structure polymer (A
The gel content of -1) is preferably 50% by weight or more, and in order to obtain excellent solvent resistance and warm water whitening resistance of the multilayer structure polymer (A-1), the gel content is 6
It is preferably at least 0% by weight.

The gel content in this case means the above-mentioned 2 of the two-layer crosslinked rubber elastic material itself, the intermediate layer polymer (A-1-d) and the outermost layer polymer (A-1-c). It contains a graft component to the layer-crosslinked rubber elastic body. The gel content referred to here is 1% by weight M of (A-1) of the multilayer structure polymer.
Prepare an EK solution and leave it at 25 ° C for 24 hours, then 1600
0r. p. % by weight of insoluble matter after centrifugation at m for 90 minutes. The component is the added weight of the two-layer crosslinked rubber elastic material and the graft layer, and it can be replaced by the graft ratio. However, since the present invention has a special structure, the gel content is used as a guide for the graft amount.

As the method for producing the multi-layer structure polymer (A-1) of the present invention, the sequential multi-stage polymerization method by emulsion polymerization is the most suitable polymerization method, but it is not particularly limited thereto, and for example, It can be carried out by emulsion suspension polymerization in which the outermost layer polymer (A-1-c) is converted into a suspension polymerization system after the emulsion polymerization.

As the acrylic resin (A) used in the present invention, the following polymer (A-2) can be used.

The polymer (A-2) is a thermoplastic polymer (A-
2-1) 0.1 to 20% by weight, rubber-containing polymer (A-2
-2) 55 to 99.9% by weight, and a thermoplastic polymer (A-2-3) 0 to 44.9% by weight, (A-2
-1), (A-2-2) and (A-2-3) are 100% by weight in total of each polymer. Further, the gel content is required to be 50% by weight or more in order to exhibit excellent matting property and bending whitening resistance. In the following (A-
Each polymer of 2-1) to (A-2-3) will be described.

The thermoplastic polymer (A-2-1) in the polymer (A-2) component is at least one other vinyl monomer copolymerizable with 50 to 100% by weight of methyl methacrylate. The polymer has a reduced viscosity (measured by dissolving 0.1 g of the polymer in 100 ml of chloroform and measuring at 25 ° C.) of more than 0.1 L / g and is important for film formability. It is a component showing a role. The reduced viscosity of the thermoplastic polymer (A-2-1) is important, and if the reduced viscosity is 0.1 L / g or less, a film with good thickness accuracy cannot be obtained. Reduced viscosity usually exceeds 0.1 L / g and 2
L / g or less, preferably 0.2 to 1.2 L / g.

In the thermoplastic polymer (A-2-1),
As a vinyl monomer that can be polymerized with methyl methacrylate, an acrylic acid alkyl ester, a methacrylic acid alkyl ester, an aromatic vinyl compound, or a vinyl cyan compound can be used.

The thermoplastic polymer (A-2-1) is preferably produced by an emulsion polymerization method, and can be recovered in powder form by a usual emulsion polymerization method and post-treatment method.

The thermoplastic polymer (A-2-1) thus obtained is used in the range of 0.1 to 20% by weight in the polymer (A-2), but has a good matting effect. It is preferable to use 3% by weight or more for the expression of sex.

The rubber-containing polymer (A-2-2) has a function of imparting excellent impact resistance and elongation to the resin composition and has a multilayer structure containing an alkyl acrylate as a rubber main component. It is a graft copolymer. Further, it is also a necessary component for exhibiting good matting properties and bending whitening resistance.

The rubber-containing polymer (A-2-2) comprises 50 to 99.9% by weight of alkyl acrylate, 0 to 40% by weight of other copolymerizable vinyl monomer, and a copolymerizable crosslinkable compound. 50-100% by weight of a methacrylic acid ester can be copolymerized with 100% by weight of an elastic copolymer obtained by polymerizing a monomer mixture consisting of 0.1-10% by weight of a monomer. It is obtained by polymerizing 10 to 2000 parts by weight of a monomer composed of 0 to 50% by weight of a vinyl monomer or a mixture thereof in at least one step.

Examples of the acrylic acid alkyl ester used here include those having an alkyl group having 1 to 8 carbon atoms, of which butyl acrylate and 2-ethylhexyl acrylate are preferred.

In obtaining the elastic copolymer, 40% by weight or less of another copolymerizable vinyl monomer can be copolymerized. As the other copolymerizable vinyl monomer used herein, methyl methacrylate, butyl methacrylate, methacrylic acid alkyl ester such as cyclohexyl methacrylate, styrene, acrylonitrile and the like are preferable.

Further, a copolymerizable crosslinkable monomer is used. The crosslinkable monomer to be used is not particularly limited, but preferably ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl. Examples thereof include isocyanurate, divinylbenzene, diallyl maleate, trimethylolpropane triacrylate, and allyl cinnamate, which can be used alone or in combination.

As the monomer to be grafted to the elastic copolymer, 50% by weight or more of alkyl methacrylate is used, and specifically, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid 2- Examples thereof include ethylhexyl and cyclohexyl methacrylate. 50% by weight of other copolymerizable vinyl monomer
The following are used and are not particularly limited, but specifically,
Examples thereof include alkyl acrylates such as methyl acrylate, butyl acrylate and cyclohexyl acrylate, styrene and acrylonitrile.

The monomer mixture to be grafted is used in an amount of 10 to 2000 parts by weight, preferably 20 to 200 parts by weight, based on 100 parts by weight of the elastic copolymer, and the polymerization can be carried out in at least one stage.

Rubber-containing polymer (A-2-2) in the present invention
Can be obtained by usual emulsion polymerization. A chain transfer agent and other polymerization aids may be used during the polymerization. Known chain transfer agents can be used, but mercaptans are preferable.

The rubber polymer (A-
In 2-2), the gel content is required to be 50% by weight or more in order to exhibit excellent matting properties and bending whitening resistance. In addition, the gel content includes an elastic copolymer and a graft component to the elastic copolymer, and a 1% by weight MEK solution of the rubber-containing polymer (A-2-2) is prepared.
After standing at 5 ° C for a whole day and night, 16000 r.p.m. p. m. 90
It is the weight percentage of insoluble matter after centrifugation for minutes.

The rubber-containing polymer (A-2-2) of the present invention is used in the range of 55 to 99.9% by weight in the polymer (A-2). It is preferably used in an amount of 60% by weight or more in order to exhibit the whitening property.

The thermoplastic polymer (A- used in the present invention
2-3) is 50 to 99% by weight of a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms, 1 to 50% by weight of an acrylic acid ester, and at least other vinyl monomer copolymerizable therewith. It is composed of 0 to 50% by weight of one kind, and the reduced viscosity of the polymer (0.1 g of the polymer is added to 100 m of chloroform.
It is a polymer which is dissolved in 1 and measured at 25 ° C.) is 0.1 L / g or less.

As the methacrylic acid ester used in the thermoplastic polymer (A-2-3), methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like can be used, but methyl methacrylate is most preferable. As the acrylic acid ester, methyl acrylate, ethyl acrylate, butyl acrylate, etc. can be used. The acrylic ester is used in the range of 0.1 to 50% by weight, preferably 0.5 to 40% by weight. Known monomers can be used as the other copolymerizable vinyl monomer.

The method for producing the thermoplastic polymer (A-2-3) is not particularly limited, but usual suspension polymerization, emulsion polymerization,
Polymerization can be performed by a method such as bulk polymerization. A chain transfer agent or other polymerization aid may be used during the polymerization. Known chain transfer agents can be used, but mercaptans are preferable.

The thermoplastic polymer (A-2-3) of the present invention is used within the range of 0 to 44.9% by weight in the polymer (A-2).

The linear polymer (B) having a hydroxyl group used in the present invention is a hydroxyalkyl acrylic acid ester having 1 to 8 carbon atoms and / or a methacrylic acid hydroxyalkyl ester (b-1) 1. ~ 80
% By weight, methacrylic acid alkyl ester having 1 to 13 carbon atoms in alkyl group (b-2) 10 to 99% by weight, acrylic acid alkyl ester having 1 to 8 carbon atoms in alkyl group (b-
3) It is obtained by polymerizing 0 to 79% by weight, and 0 to 50% by weight (b-4) of at least one other copolymerizable vinyl monomer, and has an intrinsic viscosity (chloroform as a solvent. And measured at 25 ° C.) is 0.05 to 0.3 L / g
Is in the range.

The acrylic acid hydroxyalkyl ester having 1 to 8 carbon atoms of the alkyl group used for the linear polymer (B) and / or the methacrylic acid hydroxyalkyl ester (b-1) includes methacrylic acid 2 -Hydroxyethyl, 2-hydroxypropyl methacrylate,
Examples thereof include 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate. Among these, 2-hydroxyethyl methacrylate is particularly preferable.

Acrylic acid hydroxyalkyl ester,
And / or the amount of the methacrylic acid hydroxyalkyl ester (b-1) used is in the range of 1 to 80% by weight.
If it is less than 1% by weight, the matting effect is insufficient. On the other hand, 8
If it exceeds 0% by weight, the elongation may decrease or the surface condition may become poor. The preferred range of use for manifesting the matting property is 5 to 50% by weight. More preferably 20-
It is desirable to use it in the range of 50% by weight.

Examples of the methacrylic acid alkyl ester (b-2) having 1 to 13 carbon atoms in the alkyl group used in the linear polymer (B) include lower alkyl groups such as methyl methacrylate, ethyl methacrylate and butyl methacrylate. A methacrylic acid alkyl ester is preferable, and methyl methacrylate is particularly preferable. The amount of the methacrylic acid alkyl ester used is in the range of 10 to 99% by weight. Preferably 30 to
It is desirable to use it in the range of 85% by weight.

The acrylic acid alkyl ester (b-3) having 1 to 8 carbon atoms of the alkyl group used in the linear polymer (B) can be used in the range of up to 79% by weight. Examples thereof include lower acrylic acid alkyl esters such as methyl, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. The alkyl acrylate is preferably used in the range of 0.5 to 40% by weight. More preferably, it is 5 to 25% by weight.

Further, in the linear polymer (B) of the present invention, at least one other vinyl monomer (b-4) can be used in an amount of up to 50% by weight. Specifically, known monomers can be used, for example, vinyl aromatic monomers such as styrene, vinyltoluene, α-methylstyrene, halogenated styrene, methacrylic acid, fumaric acid, maleic acid and a copolymerizable carboxylic acid. Among the esters, alkyl methacrylates having 1 to 13 carbon atoms, methacrylic acid alkyl esters, those excluding alkyl groups having 1 to 8 carbon atoms of acrylic acid alkyl esters, vinyl halides such as vinyl chloride and vinyl bromide, and vinyl acetate. And other vinyl esters, acrylonitrile and the like.

Other vinyl monomers may have better matting properties depending on the type of acrylic resin (A) in view of dispersibility. Further, in order to maintain transparency, the amount of other vinyl monomer added is adjusted to match the refractive index of the acrylic resin (A).

In the present invention, the linear polymer (D) has an intrinsic viscosity in the range of 0.05 to 0.3 L / g in order to express a certain good matteness regardless of the shaping conditions. Need to be adjusted. Specifically, a polymerization degree regulator such as mercaptan is used. As the mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like are used, but not particularly limited thereto, and known ones can be used.

The shaping conditions referred to in the present invention are the conditions of the step of melt-kneading an acrylic resin, a linear polymer, additives and the like, and the step of processing the obtained mixture into a molded product such as a film. Refers to the conditions of.

The method for producing the linear polymer (B) of the present invention is not particularly limited, but the suspension polymerization method is preferable from the viewpoint of cost.

As the initiator for suspension polymerization, those used in ordinary suspension polymerization are used, and examples thereof include organic peroxides and azo compounds.

As the suspension stabilizer, those usually used are used, and examples thereof include organic colloidal polymeric substances, inorganic colloidal polymeric substances, inorganic fine particles, and combinations of these with surfactants.

The suspension polymerization is usually carried out by suspending the monomers in an aqueous suspension together with a polymerization initiator in the presence of a suspension stabilizer. In addition to this, a polymer soluble in a monomer may be dissolved in the monomer and used.

The amount of the linear polymer (B) thus obtained is 1 to 100 parts by weight of the acrylic resin (A).
It is in the range of 40 parts by weight. In order to obtain a good matting property, it is preferable to use 2.0 parts by weight or more.

The thermoplastic resin composition (I) of the present invention can be mixed by passing it through a screw type extruder in which the mixture is simultaneously shear-compressed, kneading between heating rolls, a Burberry type mixer, or the like. Suitable methods such as mixing in a heated high shear mixer are commonly used.

The thermoplastic resin composition (I) of the present invention contains a general compounding agent such as a stabilizer, a lubricant, a processing aid, an impact resistance aid, a plasticizer, a foaming agent, a filler and a colorant, if necessary. And the like. The resin composition (I) of the present invention thus obtained can be easily molded into a film, sheet or the like by a usual method such as a T-die method, an inflation method, a calender method, an extrusion molding method and the like.

Further, a laminate having the thermoplastic resin composition (I) as a surface layer can be produced. As the base material on which the thermoplastic resin composition (I) is laminated, known resins can be used, but acrylic resin, polycarbonate resin, vinyl chloride resin, and ABS resin are preferable from the viewpoint of heat fusion property.

However, a base material such as resin, wood, steel plate or the like which is not heat-sealed can be bonded by using an adhesive.

The method for producing a laminate using the thermoplastic resin composition (I) includes, for example, a method of forming one molded article and then casting a solution containing another polymer to remove the solvent. Known laminating methods can be adopted without limitation, but a coextrusion method using an extruder, an extrusion lamination method, and a thermal lamination method using a heating roll are preferable.

In the laminate of the present invention, an intermediate layer can be provided between the thermoplastic resin composition (I) for the surface layer and the thermoplastic resin for the substrate.

Further, the thermoplastic resin composition and the laminate having excellent matting properties can be easily printed and their design effect can be remarkably enhanced.

[0084]

The present invention will be described in more detail with reference to the following examples. The evaluation methods and devices used in the examples are as follows.

(1) The evaluation of matting property is ASTM-D52
3 compliant with Murakami Color Research Laboratory gloss meter GM-26D
Was used to measure 60 degree surface gloss.

(2) The intrinsic viscosity and reduced viscosity were measured at 25 ° C. using chloroform as a solvent, using an AVL-2C automatic viscometer manufactured by San Denshi Kogyo. In addition, in the measurement of reduced viscosity, 0.1 ml of the sample was added to 100 ml of chloroform.
What melt | dissolved g was used. Equipment: Twin-screw extruder PCM-30 manufactured by Ikegai Tekko Co., Ltd. Single-screw extruder Tanabe Plastic Machinery Co., Ltd. VS-40 Film-forming machine 1 40mm single-screw extruder using 300mm T-die Film-forming machine 2 65mm single-screw extruder 900 mm T die used for (3) Appearance: The surface condition (roughness, uniformity) was visually evaluated as a guide for evaluation of dispersibility.

◯: Very good Δ: Normal ×: Poor (Example 1) (1) Production of linear polymer (B) having hydroxyl group Reaction with stirrer, reflux condenser, nitrogen gas inlet, etc. The container was charged with the following mixture.

Methyl acrylate 20 parts by weight Methyl methacrylate 60 parts by weight 2-Hydroxyethyl methacrylate 20 parts by weight n-octyl mercaptan 0.08 parts by weight Lauroyl peroxide 1 part by weight Calcium triphosphate 5 parts by weight Deionized water 250 parts by weight After thoroughly substituting the inside of the vessel with nitrogen gas, the mixture of the above mixture was heated to 75 ° C. with stirring, and the polymerization was advanced in a nitrogen gas stream. After 2 hours, the temperature was raised to 90 ° C and further 4
After 5 minutes, the polymerization was completed, dehydrated and dried to obtain a linear polymer (B).

The intrinsic viscosity of this linear polymer was measured and found to be 0.11 L / g.

(2) Production of multi-layered polymer (A-1) 250 parts by weight of ion-exchanged water in a polymerization vessel equipped with a cooler,
2 parts by weight of ester soda salt of sulfosuccinic acid, 0.05 parts by weight of sodium formaldehyde sulfoxylate were charged, and after stirring under nitrogen, 1.6 parts by weight of methyl methacrylate, 8 parts by weight of n-butyl acrylate, dimethacrylic acid. A mixture of 0.4 parts by weight of 1,3 butylene glycol, 0.1 parts by weight of allyl methacrylate, and 0.04 parts by weight of cumene hydroperoxide is charged. 7
After the temperature was raised to 0 ° C., the reaction was continued for 60 minutes and the innermost layer polymer (A
The polymerization of -1-a) is completed. Subsequently, methyl methacrylate 1.5 forming a crosslinked elastic polymer (A-1-b)
60 parts by weight of a mixture consisting of 22.5 parts by weight of butyl acrylate, 1.0 part by weight of 1,3 butylene glycol dimethacrylate, 0.25 parts by weight of allyl methacrylate, and 0.05 parts by weight of cumene hydroperoxide. Polymerization was carried out by adding for 2 minutes to obtain a two-layer crosslinked rubber elastic body.

The swelling degree and gel content of the obtained two-layer crosslinked rubber elastic body were determined by the above-mentioned methods, and were 1 respectively.
It was 0% by weight and 90% by weight.

Subsequently, a mixture of 5 parts by weight of methyl methacrylate, 5 parts by weight of butyl acrylate and 0.1 parts by weight of allyl methacrylate was reacted as the intermediate layer (A-1-d), and finally the outermost layer polymer ( A-1-c) 52.25 parts by weight of methyl methacrylate, butyl acrylate
Polymerization was completed by reacting a mixture having a composition of 2.75 parts by weight. The obtained polymer emulsion was used as polymer 10
5 parts by weight of calcium chloride based on 0 parts by weight was salted out, washed, and dried to obtain a multilayer structure polymer (A-1).

(3) Production of thermoplastic resin composition (I) 100 parts by weight of the multilayer structure polymer obtained in Example 1 (2) was used to obtain the linear chain obtained in Example 1 (1). 10 parts by weight of the polymer (B) was blended and mixed, and the mixture was extruded and cut into pellets under the conditions of a device temperature setting of 240 ° C. and a discharge rate of about 4 kg / hr using a twin-screw extruder. The obtained pellets are dried and then subjected to T-die method using a film forming machine 1
The film was formed at 40 ° C. and evaluated as a film having a thickness of about 50 μm. The results are shown in Table 1.

[0094]

[Table 1]

(4) In the first embodiment (3), the discharge amount is about 8
An experiment was conducted in the same manner as in Example 1 (3) except that the amount was changed to kg / hr. The results are shown in Table 1.

(5) An experiment was conducted in the same manner as in Example 1 (3) except that the apparatus temperature was set to 220 ° C. and the discharge rate was changed to about 8 kg / hr in Example 1 (3). The results are shown in Table 1.

(6) Example 1 (3) except that the twin-screw extruder is changed to a single-screw extruder in Example 1 (3), the apparatus temperature is set to 250 ° C., and the discharge rate is changed to about 7 kg / hr. An experiment was conducted in the same manner as in. The results are shown in Table 1.

(7) An experiment was conducted in the same manner as in Example 1 (6) except that the discharge rate in Example 1 (6) was changed to about 14 kg / hr. The results are shown in Table 1.

(8) An experiment was conducted in the same manner as in Example 1 (6) except that the apparatus temperature setting in Example 1 (6) was changed to 220 ° C. and the discharge rate was changed to about 14 kg / hr. Table 1 shows the results
Shown in

(9) An experiment was conducted in the same manner as in Example 1 (4) except that the film forming machine 2 was used instead of using the film forming machine 1 in Example 1 (4). The results are shown in Table 1.

(Example 2) (1) Example 1 Example 1 (1) except that the compounding amount of n-octyl mercaptan was changed to 0.15 parts by weight.
The experiment was conducted in the same manner as (1). When the intrinsic viscosity of the obtained linear polymer was measured, it was 0.069 L / g.

(2) Production of Thermoplastic Resin Composition (I) In Example 1 (3), instead of the linear polymer obtained in Example 1 (1), Example 2 (1) was used. An experiment was conducted in the same manner as in Example 1 (3) except that the obtained linear polymer was used. The results are shown in Table 1.

(3) An experiment was conducted in the same manner as in Example 2 (2) except that the discharge rate in Example 2 (2) was changed to about 8 kg / hr. The results are shown in Table 1.

(4) An experiment was conducted in the same manner as in Example 2 (2) except that the apparatus temperature setting was changed to 220 ° C. and the discharge rate was changed to about 8 kg / hr in Example 2 (2). The results are shown in Table 1.

(5) Example 2 (2) Except that the twin-screw extruder was changed to a single-screw extruder, the apparatus temperature setting conditions were changed to 250 ° C., and the discharge rate was changed to about 7 kg / hr. )
An experiment was performed in the same manner as in the above. The results are shown in Table 1.

(6) An experiment was conducted in the same manner as in Example 2 (5) except that the discharge rate was changed to about 14 kg / hr in Example 2 (5). The results are shown in Table 1.

(7) An experiment was conducted in the same manner as in Example 2 (5) except that the apparatus temperature setting was changed to 220 ° C. and the discharge rate was changed to about 14 kg / hr in Example 2 (5). Table 1 shows the results
Shown in

(8) An experiment was conducted in the same manner as in Example 2 (3) except that the film forming machine 2 was used instead of using the film forming machine 1 in Example 2 (3). The results are shown in Table 1.

Example 3 (1) Production of Thermoplastic Polymer (A-2-1) 200 parts by weight of ion-exchanged water substituted with nitrogen was charged into a reaction vessel, and 1 part by weight of emulsifier potassium oleate and potassium persulfate were charged. 0.3 parts by weight were charged. Subsequently, 40 parts by weight of methyl methacrylate, 10 parts by weight of n-butyl acrylate, and 0.005 parts by weight of n-octyl mercaptan were charged, and the polymerization was completed by stirring at 65 ° C. for 3 hours in a nitrogen atmosphere. Subsequently, 48 parts by weight of methyl methacrylate, acrylic acid n
A monomer mixture consisting of 2 parts by weight of butyl was added dropwise over 2 hours, and after completion of the addition, the mixture was maintained for 2 hours to complete the polymerization. The obtained latex was added to a 0.25 wt% sulfuric acid aqueous solution, and the polymer was acid-deposited, dehydrated, washed with water and dried to recover the polymer in a powder form. The reduced viscosity of the obtained polymer is 0.3.
It was 8 L / g.

(2) Production of rubber-containing polymer (A-2-2) The following proportions of raw materials were charged in a reaction vessel, and the polymerization was completed while stirring at 50 ° C. for 4 hours in a nitrogen atmosphere.
An elastic latex was obtained.

Butyl acrylate 77 parts by weight Styrene 22.7 parts by weight Allyl methacrylate 0.3 parts by weight Sodium dioctyl sodium sulfosuccinate 2.0 parts by weight Deionized water 300 parts by weight Potassium persulfate 0.3 parts by weight This elastic latex 100 parts by weight (as a solid content) was placed in a reaction vessel, and the atmosphere was sufficiently replaced with nitrogen while stirring.
The temperature was raised to 0 ° C., 0.125 parts by weight of sodium formaldehyde sulfoxylate and 2 parts by weight of deionized water were added, and then 60 parts by weight of methyl methacrylate and n-octyl mercaptan were added while keeping the temperature at 80 ° C. .0
5 parts by weight, t-butyl hydroperoxide 0.12
A mixture consisting of 5 parts by weight was added dropwise over 2 hours and then kept for 2 hours to complete the polymerization. The obtained copolymer latex was salted out, dehydrated, washed with water and washed to obtain a rubber-containing polymer in powder form.

(3) Production of thermoplastic resin composition (I) As described above, 10 parts by weight of the linear polymer (B) obtained in Example 1 (1) and Example 3 (1) were used. ) 5% by weight of the thermoplastic polymer (A-2-1), 45% by weight of the rubber-containing polymer (A-2-2) obtained in Example (2), methyl methacrylate / acrylic acid Thermoplastic polymer (A-2) which is a methyl copolymer (methyl methacrylate / methyl acrylate = 90/10, reduced viscosity = 0.051 L / g)
-3) 100 parts by weight of polymer (A-2) consisting of 50% by weight was mixed with a Henschel mixer. Using a twin-screw extruder, this mixture was set at a temperature of 240 ° C. and a discharge rate of about 4
It was extruded and cut into pellets under the condition of kg / hr.
The obtained pellets are dried and then used in the film forming machine 1 to
A film was formed at 40 ° C. to obtain a 50 μm film. Table 1 shows the evaluation results.

(4) An experiment was conducted in the same manner as in Example 3 (3) except that the discharge rate was changed to about 8 kg / hr in Example 3 (3). The results are shown in Table 1.

(5) An experiment was conducted in the same manner as in Example 3 (3) except that the apparatus temperature setting was changed to 220 ° C. and the discharge rate was changed to about 8 kg / hr in Example 3 (3). The results are shown in Table 1.

(6) Example 3 (3) except that the twin-screw extruder is changed to a single-screw extruder in Example 3 (3), the apparatus temperature is set to 250 ° C., and the discharge rate is changed to about 7 kg / hr. An experiment was conducted in the same manner as in. The results are shown in Table 1.

(7) An experiment was conducted in the same manner as in Example 3 (6) except that the discharge rate in Example 3 (6) was changed to about 14 kg / hr. The results are shown in Table 1.

(8) An experiment was conducted in the same manner as in Example 3 (6) except that the apparatus temperature setting in Example 3 (6) was changed to 220 ° C. and the discharge rate was changed to about 14 kg / hr. Table 1 shows the results
Shown in

(9) An experiment was conducted in the same manner as in Example 3 (4) except that the film forming machine 2 was used instead of using the film forming machine 1 in Example 3 (4). The results are shown in Table 1.

Example 4 (1) Manufacture of Laminated Polymer Multilayer Structure Polymer (A-1) 1 Obtained in Example 1 (2)
10 parts by weight of the linear polymer (B) obtained in Example 1 (1) was mixed and mixed with 00 parts by weight, and the mixture was extruded and cut at 240 ° C. with a twin-screw extruder to form pellets. did. After drying the obtained pellets, a thermoplastic resin (I) layer having a matting property by a coextrusion molding method was formed with an acrylic resin pellet (Acrypet VH manufactured by Mitsubishi Rayon) to 100 μm,
A laminate was obtained by molding at 240 ° C. so that the acrylic resin layer had a thickness of 2 mm. The evaluation results of the laminate are shown in Table 2.

[0120]

[Table 2]

(2) An experiment was conducted in the same manner as in Example 4 (1) except that the discharge rate of the thermoplastic resin (I) at the time of extrusion was changed to about 8 kg / hr in Example 4 (1). Table 2 shows the results.

(3) Same as Example 4 (1) except that the apparatus temperature setting during extrusion of the thermoplastic resin (I) in Example 4 (1) was changed to 220 ° C. and the discharge rate was changed to about 8 kg / hr. The experiment was conducted. Table 2 shows the results.

(4) In Example 4 (1), the twin-screw extruder at the time of extruding the thermoplastic resin (I) was changed to a single-screw extruder, the device temperature was set to 250 ° C., and the discharge rate was set to about 7 kg / hr. An experiment was conducted in the same manner as in Example 4 (1) except that the change was made.
Table 2 shows the results.

(5) An experiment was conducted in the same manner as in Example 4 (4) except that the discharge rate of the thermoplastic resin (I) at the time of extrusion was changed to about 14 kg / hr in Example 4 (4). Table 2 shows the results.

(6) Example 4 (4) except that the apparatus temperature setting during extrusion of the thermoplastic resin (I) in Example 4 (4) was changed to 220 ° C. and the discharge rate was changed to about 14 kg / hr.
An experiment was performed in the same manner as in the above. Table 2 shows the results.

(Example 5) (1) The film obtained in Example 1 (3) was heat-laminated using a laminating roll with embossing and a soft vinyl chloride film having a thickness of 100 µ under the conditions of 150 ° C and 30 kg / cm ^2. Then, a laminate was obtained. Table 2 shows the results. (2) An experiment similar to that in Example 5 (1) except that the film obtained in Example 1 (4) was used in place of the film obtained in Example 1 (3) in Example 5 (1). I went. Table 2 shows the results.

(3) Example 5 Example 1 in (1)
An experiment was conducted in the same manner as in Example 5 (1) except that the film obtained in Example 1 (5) was used instead of the film obtained in (3). Table 2 shows the results.

(4) Example 5 Example 1 in (1)
An experiment was conducted in the same manner as in Example 5 (1) except that the film obtained in Example 1 (6) was used instead of the film obtained in (3). Table 2 shows the results.

(5) Example 5 Example 1 in (1)
An experiment was conducted in the same manner as in Example 5 (1) except that the film obtained in Example 1 (7) was used instead of the film obtained in (3). Table 2 shows the results.

(6) Example 5 Example 1 in (1)
An experiment was conducted in the same manner as in Example 5 (1) except that the film obtained in Example 1 (8) was used instead of the film obtained in (3). Table 2 shows the results.

(7) Example 5 Example 1 in (1)
An experiment was conducted in the same manner as in Example 5 (1) except that the film obtained in Example 1 (9) was used instead of the film obtained in (3). Table 2 shows the results.

Example 6 (1) Manufacture of Laminate A linear polymer obtained in Example 1 (1) was added to 100 parts by weight of the polymer (A-2) in Example 3 (3). Combine (B) 1
0 parts by weight were blended and mixed, and the mixture was extruded and cut into pellets with a twin-screw extruder at a device temperature setting of 240 ° C. and a discharge rate of about 4 kg / hr. After drying the obtained pellets, acrylic resin pellets (Acrypet V manufactured by Mitsubishi Rayon Co., Ltd.)
H) was molded at 240 ° C. by a coextrusion molding method so that the thermoplastic resin (I) layer having a matting property was 100 μm and the acrylic resin layer was 2 mm to obtain a laminate. The evaluation results of the laminate are shown in Table 2.

(2) An experiment was conducted in the same manner as in Example 6 (1) except that the discharge rate of the thermoplastic resin (I) at the time of extrusion was changed to about 8 kg / hr in Example 6 (1). Table 2 shows the results.

(3) Same as Example 6 (1) except that the apparatus temperature setting during extrusion of the thermoplastic resin (I) in Example 6 (1) is changed to 220 ° C. and the discharge rate is changed to about 8 kg / hr. The experiment was conducted. Table 2 shows the results.

(4) In Example 6 (1), the twin-screw extruder for the thermoplastic resin (I) was changed to a single-screw extruder, the device temperature was changed to 250 ° C., and the discharge rate was changed to about 7 kg / hr. The experiment was performed in the same manner as in Example 6 (1) except for the above. Table 2 shows the results
Shown in

(5) An experiment was conducted in the same manner as in Example 6 (4) except that the discharge rate of the thermoplastic resin (I) at the time of extrusion was changed to about 14 kg / hr in Example 6 (4). Table 2 shows the results.

(6) Example 6 (4) except that the apparatus temperature setting during extrusion of the thermoplastic resin (I) in Example 6 (4) was changed to 220 ° C. and the discharge rate was changed to about 14 kg / hr.
An experiment was performed in the same manner as in the above. Table 2 shows the results.

Comparative Example 1 (1) Production of Linear Polymer (B) A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, etc. was charged with the following mixture.

Methyl acrylate 20 parts by weight Methyl methacrylate 60 parts by weight 2-hydroxyethyl methacrylate 20 parts by weight t-dodecyl mercaptan 0.5 parts by weight Lauroyl peroxide 1 part by weight Calcium triphosphate 5 parts by weight Deionized water 250 parts by weight After thoroughly substituting the inside of the vessel with nitrogen gas, the mixture of the above mixture was heated to 75 ° C. with stirring, and the polymerization was advanced in a nitrogen gas stream. After 3 hours, the temperature was raised to 90 ° C and further 4
Polymerization was completed by holding for 5 minutes, dehydrated and dried to obtain a hydroxyl group-containing polymer. The intrinsic viscosity of the obtained hydroxyl group-containing polymer was measured and found to be 0.04 L / g. (2) Example 1 except that the linear polymer obtained in Example 1 (1) in Example 1 (3) is changed to the linear polymer obtained in Comparative Example 1 (1). The experiment was conducted in the same manner as (3). The results are shown in Table 3.

[0140]

[Table 3]

(3) Example 1 Example 1 in (4)
An experiment was performed in the same manner as in Example 1 (4), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 3.

(4) Example 1 Example 1 in (5)
An experiment was conducted in the same manner as in Example 1 (5), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 3.

(5) Example 1 Example 1 in (6)
An experiment was conducted in the same manner as in Example 1 (6), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 3.

(6) Example 1 Example 1 in (7)
An experiment was conducted in the same manner as in Example 1 (7), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 3.

(7) Example 1 Example 1 in (8)
An experiment was conducted in the same manner as in Example 1 (8), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 3.

(8) Example 1 Example 1 in (9)
An experiment was conducted in the same manner as in Example 1 (9), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 3.

Comparative Example 2 (1) The following mixture was charged in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.

Methyl acrylate 10 parts by weight Methyl methacrylate 70 parts by weight 2-hydroxyethyl methacrylate 20 parts by weight n-octyl mercaptan 0.35 parts by weight Lauroyl peroxide 1 part by weight Calcium triphosphate 5 parts by weight Deionized water 250 parts by weight After sufficiently substituting the interior of the vessel with nitrogen gas, the mixture of the above mixture was heated to 7 ° C. with stirring, and the polymerization was advanced in a nitrogen gas stream. After 3 hours, the temperature was raised to 90 ° C and further 45
Polymerization was completed by holding for minutes, dehydration and drying were performed to obtain a hydroxyl group-containing polymer.

The intrinsic viscosity of the obtained hydroxyl group-containing polymer was measured and found to be 0.045 L / g.

(2) Example 3 Example 3 in (3)
An experiment was performed in the same manner as in Example 3 (3) except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 3.

(3) Example 3 Example 3 in (4)
An experiment was conducted in the same manner as in Example 3 (4), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 3.

(4) Example 3 Example 3 in (5)
An experiment was conducted in the same manner as in Example 3 (5), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 3.

(5) Example 3 Example 3 in (6)
An experiment was conducted in the same manner as in Example 3 (6), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 3.

(6) Example 3 Example 3 in (7)
An experiment was conducted in the same manner as in Example 3 (7) except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 3.

(7) Example 3 Example 3 in (8)
An experiment was conducted in the same manner as in Example 3 (8) except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 3.

(8) Example 3 Example 3 in (9)
An experiment was performed in the same manner as in Example 3 (9), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 3.

Comparative Example 3 (1) Manufacture of Laminate In Example 4 (1), the linear polymer obtained in Example 1 (1) was directly obtained in Comparative Example 1 (1). An experiment was conducted in the same manner as in Example 4 (1) except that the chain polymer was used to obtain a laminate. The evaluation results of the laminate are shown in Table 4.

[0158]

[Table 4]

(2) Example 4 Example 1 in (2)
An experiment was conducted in the same manner as in Example 4 (2), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 4.

(3) Example 4 Example 1 in (3)
An experiment was conducted in the same manner as in Example 4 (3), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 4.

(4) Example 4 Example 1 in (4)
An experiment was performed in the same manner as in Example 4 (4), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 4.

(5) Example 4 Example 1 in (5)
An experiment was conducted in the same manner as in Example 4 (5), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 4.

(6) Example 4 Example 1 in (6)
An experiment was conducted in the same manner as in Example 4 (6) except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 1 (1). The results are shown in Table 4.

Comparative Example 4 (1) In Example 6 (1), the linear polymer obtained in Example 1 (1) was changed to the linear polymer obtained in Comparative Example 2 (1). An experiment was conducted in the same manner as in Example 6 (1) except that the layered product was obtained. The evaluation results of the laminate are shown in Table 4. (2) Example 6 except that the linear polymer obtained in Example 1 (1) in Example 6 (2) is changed to the linear polymer obtained in Comparative Example 2 (1). The experiment was conducted in the same manner as (2). The results are shown in Table 4.

(3) Example 6 Example 1 in (3)
An experiment was performed in the same manner as in Example 6 (3), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 4.

(4) Example 6 Example 1 in (4)
An experiment was performed in the same manner as in Example 6 (4), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 4.

(5) Example 6 Example 1 in (5)
An experiment was performed in the same manner as in Example 6 (5), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 4.

(6) Example 6 Example 1 in (6)
An experiment was performed in the same manner as in Example 6 (6), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 2 (1). The results are shown in Table 4.

Comparative Example 5 (1) Production of Linear Polymer (B) The following mixture was charged in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet and the like.

Methyl acrylate 20 parts by weight Methyl methacrylate 60 parts by weight 2-hydroxyethyl methacrylate 20 parts by weight n-octyl mercaptan 0.01 parts by weight Lauroyl peroxide 1 part by weight Calcium triphosphate 5 parts by weight Deionized water 250 parts by weight After sufficiently substituting the inside of the vessel with nitrogen gas, the mixture of the above mixture was heated to 70 ° C. with stirring, and the polymerization was advanced in a nitrogen gas stream. After 2 hours, the temperature was raised to 90 ° C and further 4
Polymerization was completed by holding for 5 minutes, dehydrated and dried to obtain a hydroxyl group-containing polymer. The intrinsic viscosity of the obtained hydroxyl group-containing polymer was measured and found to be 0.4 L / g.

(2) Example 1 Example 1 in (3)
An experiment was conducted in the same manner as in Example 1 (3), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 5 (1). The results are shown in Table 4.

(3) Example 1 Example 1 in (4)
An experiment was conducted in the same manner as in Example 1 (4) except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 5 (1). The results are shown in Table 4.

(4) Example 1 Example 1 in (5)
An experiment was conducted in the same manner as in Example 1 (5) except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 5 (1). The results are shown in Table 4.

(5) Example 1 Example 1 in (6)
An experiment was conducted in the same manner as in Example 1 (6), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 5 (1). The results are shown in Table 4.

(6) Example 1 Example 1 in (7)
An experiment was conducted in the same manner as in Example 1 (7) except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 5 (1). The results are shown in Table 4.

(7) Example 1 Example 1 in (8)
An experiment was performed in the same manner as in Example 1 (8), except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 5 (1). The results are shown in Table 4.

(8) Example 1 Example 1 in (9)
An experiment was conducted in the same manner as in Example 1 (9) except that the linear polymer obtained in (1) was changed to the linear polymer obtained in Comparative Example 5 (1). The results are shown in Table 4.

[0178]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention exhibits good matting properties regardless of the shaping conditions, as compared with the case of using a conventional matting agent. Play.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area // (C08L 33/06 33:14)

Claims (6)

[Claims] 1. A linear polymer (B) having a hydroxyl group shown below, relative to 100 parts by weight of an acrylic resin (A).
A matte thermoplastic resin composition (I) containing 40 parts by weight. (B) Linear Polymer Having Hydroxyl Group Acrylic hydroxyalkyl ester having 1 to 8 carbon atoms of alkyl group, and / or methacrylic acid hydroxyalkyl ester (b-1) 1 to 80% by weight, carbon of alkyl group 10 to 99% by weight of a methacrylic acid alkyl ester (b-2) having a number of 1 to 13, and an acrylic acid alkyl ester (b-3) having a carbon number of 1 to 8 (b-3) of an alkyl group
It is obtained by polymerizing 9% by weight, and 0 to 50% by weight (b-4) of at least one other copolymerizable vinyl monomer, and has an intrinsic viscosity (chloroform as a solvent at 25 ° C.). Linear polymer having a hydroxyl group in the range of 0.05 to 0.3 L / g. 2. A film-like material having a thickness of 5 to 300 μm, which is obtained by molding the thermoplastic resin composition (I) according to claim 1. 3. A laminate comprising the film-like product according to claim 2 as a surface layer. 4. The laminate according to claim 3, which is laminated by a coextrusion method. 5. The laminate according to claim 3, which is laminated by an extrusion lamination method. 6. The laminate according to claim 3, which is laminated by a thermal lamination method.