JPH07238202A - Thermoplastic resin composition and its laminate - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent flatting and a laminate. CONSTITUTION:This thermoplastic resin composition comprises (A) 100 pts.wt. of an acrylic resin and (B) 1-40 pts.wt. of a hydroxyl group-containing straight- chain polymer composed of (b-1) 1-80 pts.wt. of a 1-8C alkyl group-containing acrylic acid hydroxyalkyl ester or methacrylic acid hydroxylalkyl ester, (b-2) 10-99wt.% of a 1-13C alkyl group-containing methacrylic acid alkyl ester, (b-3) 0-70wt.% of a 1-8C alkyl group-containing acrylic acid alkyl ester and 0-50wt.% of at least one of other copolymerizable vinyl monomers. A laminate having a filmy material on the surface layer is obtained from this thermoplastic resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent matting properties and a laminate thereof.

[0002]

2. Description of the Related Art Generally, a resin molded article has a luster, which is an important characteristic depending on the intended use, but on the other hand, there are many applications where such a lusterless article is preferred. Matting properties are particularly preferred for applications such as vehicle interior materials, furniture and housings for electric devices, and wallpapers.

[0003] The conventional matting methods for thermoplastic resins are roughly classified into (1) a method by imprinting and matting, and (2)
It can be divided into the methods of adding an inorganic or organic matting agent. The method (1) generally has the advantage of less deterioration of physical properties, but has poor productivity and high processing cost, and also has an insufficient matte effect, and is often unsuitable for secondary processing applications. . On the contrary, the method (2) 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 big problem of deterioration of physical properties. . In particular, when an inorganic material such as silica gel is used as a matting agent, the physical properties such as impact resistance and strength and elongation are significantly deteriorated.

On the other hand, a method using an organic substance, especially a high-molecular matting agent is disclosed in JP-A-56-36535, which is an average particle size of 35 to 500 .mu.m obtained by suspension polymerization. This is a method using a cross-linked polymer.

[0005]

However, in the method of using the above-mentioned high-molecular matting agent, the deterioration of the physical properties such as impact resistance and strength elongation is small, but the matting effect is insufficient. . In addition, when a resin using the polymer is shaped into a film, it is relatively easy to generate spots. The present invention aims to solve these problems.

[0006]

That is, the present invention provides 100% by weight of an acrylic resin (A) and a hydroxyalkyl acrylate or hydroxyalkyl methacrylate (b-1) having an alkyl group having 1 to 8 carbon atoms.
Methacrylic acid alkyl ester (b-2) 10-99 having 1 to 80% by weight and an alkyl group having 1 to 13 carbon atoms
% By weight, 0 to 79% by weight of alkyl acrylate (b-3) having an alkyl group having 1 to 8 carbon atoms, and at least one other copolymerizable vinyl monomer 0 to 50
1% by weight of linear polymer (B) having a hydroxyl group
A laminate comprising a thermoplastic resin composition comprising 40 parts by weight and a film-like product obtained from the thermoplastic resin composition in a surface layer.

As the acrylic resin (A) used in the present invention, known ones can be used, and among the acrylic resins, the following multilayer structure polymers (C) and polymers (D) exhibit particularly matte properties. Is excellent.

The monomer composition used in the multilayer structure polymer (C) is shown below.

As the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms which constitutes the innermost layer polymer (Ca), methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid 2 -Ethylhexyl, n-octyl acrylate, etc. may be used alone or as a mixture, but those having a low Tg are preferable. As the methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like are used alone or in combination. These (meth) acrylic acid alkyl esters (c-a1) are 80 to 100% by weight.
Used in the range of. Further, these (meth) acrylic acid alkyl esters are most preferably used in a unified manner in multiple stages thereafter, but depending on the final purpose, two or more types of monomers may be mixed, or other types of (meth) acrylic acid alkyl ester may be used. Esters can be used.

A monomer having a double bond capable of copolymerization (c
As -a2), acrylic acid higher alkyl ester, acrylic acid lower alkoxy ester, acrylic acid cyanoethyl ester, acrylamide, acrylic acid, methacrylic acid and other acrylic monomers are preferable, and 0 to 20% by weight is preferable.
Used in the range of. Styrene, alkyl-substituted styrene, etc. within the range of not exceeding 20% by weight in the component (Ca).
Acrylonitrile, methacrylonitrile, etc. can be used.

As the polyfunctional monomer (c-a3), ethylene glycol dimethacrylate and dimethacrylic acid 1.3 are used.
-Dimethacrylic acid alkylene glycol esters such as butylene glycol, dimethacrylic acid 1.4-butylene glycol and propylene glycol dimethacrylate are preferred, and polyvinylbenzene such as divinylbenzene and trivinylbenzene and diacrylic acid alkylene glycol esters can also be used. Is. These monomers work effectively for bridging the layer in which they are contained, and do not act for bonding between other layers. Even if the polyfunctional monomer (c-a3) is not used at all, it gives a fairly stable multilayer structure as long as the graft crossing agent is present, but depending on the purpose of addition such as when hot strength is strictly required. However, the use range is 0 to 10% by weight.

As the graft crossing agent, copolymerizable α, β
An allyl, methallyl or crotyl ester of an unsaturated carboxylic acid or dicarboxylic acid, preferably acrylic acid,
Mention may be made of allyl esters of methacrylic acid, maleic acid and 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 very important and is 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 above components (c-a1) to (c-a3). Used in the range of parts by weight. When the amount used is 0.1 parts by weight or less, the effective amount of graft bond is small, and when the amount used exceeds 5 parts by weight, the reaction amount with the crosslinked elastic polymer (Cb) polymerized and formed in the second stage is large. This causes a decrease in elasticity of the two-layer crosslinked rubber elastic body having the two-layer elastic body structure, which is one of the features of the present invention.

The content of the innermost layer polymer (C-a) in the multilayer structure polymer (C) of the present invention is 5 to 35% by weight, preferably 5 to 15% by weight. It is preferably lower than the content of b).

Next, the crosslinked elastic body (C-b) constituting the multilayer structure polymer (C) is a main component which imparts rubber elasticity to the multilayer structure polymer, and constitutes (c-b1) to (c-b1).
As the component (c-b3), the graft crossing agent and the like, those used in the above-mentioned innermost layer polymers (c-a1) to (c-a3) are used. The component (c-b1) is 80 to 10
0% by weight, component (c-b2) is 0 to 20% by weight, (c-
The component b3) is 0 to 10% by weight, and the graft crossing agent is (c-
It is used in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of b1) to (c-b3).

The content of the crosslinked elastic polymer (Cb) in the multilayer structure polymer (C) of the present invention is preferably in the range of 10 to 45% by weight, and the content of the innermost layer polymer (Ca) is contained. It is preferably higher than the amount.

The two-layer crosslinked rubber elastic body has a gel content of 85% or more and a swelling degree of 3 to 13 determined by the following measuring method.
In order to obtain excellent solvent resistance and water whitening resistance, it is necessary to be set within the range.

(Measuring method of gel content and swelling degree) JIS
According to K-6388, a predetermined amount of a two-layer crosslinked rubber elastic polymer was sampled, and methyl ethyl ketone (hereinafter ME
(Abbreviated as K)
After the EK is wiped off, its weight is measured, and then the MEK is removed in a vacuum dryer to obtain a constant weight of absolute dry weight, which is 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 (C-c) constituting the multilayer structure polymer (C) of the present invention is involved in distributing moldability and mechanical properties to the multilayer structure polymer, As the components (c-c1) and (c-c2) constituting this, those equivalent to the components (c-a1) and (c-a2) described above are used. The component (c-c1) is used in the range of 51 to 100% by weight, and the component (c-c2) is used in the range of 0 to 49% by weight. In addition, the outermost layer polymer (C-c) alone T
In order to obtain excellent solvent resistance and water whitening resistance, g must be 60 ° C. or higher, preferably 80 ° C. or higher. When the Tg of the polymer (C-c) alone is less than 60 ° C., the solvent resistance and the water whitening resistance thereof are not excellent even if the gel content of the final polymer described later is 50% or more.

The content of the outermost layer polymer (C-c) in the multilayer elastic polymer (C) of the present invention is 10 to 80% by weight, preferably 40 to 60% by weight.

The multilayer structure polymer (C) of the present invention has the above-mentioned innermost layer polymer (Ca), crosslinked elastic polymer (Cb) and outermost layer polymer (Cc) as a basic structure, Further, 10 to 9 are provided between the polymer (C-b) layer and the polymer (C-c) layer.
Acrylic acid alkyl ester having 0 part of C1-C8 alkyl group (c-d1), 90-10 wt% of methacrylic acid alkyl ester having C1-C4 alkyl group (c-d2), 0 ~ 20 wt% copolymerizable 2
0.1 to 5 parts by weight of a graft crossing agent based on 100 parts by weight of the total amount of the monomer (c-d3) having a heavy bond and the multifunctional monomer (c-d4) of 0 to 10% by weight. In the intermediate layer (C-d) having the composition described above, the amount of the alkyl acrylate ester in the intermediate layer (C-d) is monotonous from the crosslinked elastic polymer (C-b) to the outermost layer (C-c). At least one layer is arranged so as to decrease. Where (cd
The components 1) to (c-d4) and the graft crossing agent are the same as the components used in the innermost layer polymer (Ca). The graft crossing agent used in the intermediate layer (C-d) is indispensable for tightly bonding the polymer layers to obtain various excellent properties.

The content of the intermediate layer (C-d) in the multilayer structure polymer (C) of the present invention is 5 to 35% by weight, and 5% by weight.
If it is less than 50% by weight, the function as an intermediate layer is lost, and if it exceeds 35% by weight, the balance of the final polymer is lost, which is not preferable.

The multilayer structure polymer (C) of the present invention comprises the above-mentioned (C-a), (C-b), (C-c) and (C-d).
The multi-layered polymer is used for the thermoplastic resin comprising the multi-layered polymer and the copolymer (B) having a hydroxyl group to exhibit excellent matting properties. The gel content of is preferably 50% or more. Further, in order for the multilayer structure polymer to have excellent solvent resistance and water whitening resistance, the gel content must be 50%, preferably 60% or more. The gel content in this case includes the two-layer crosslinked rubber elastic body itself and the graft components of the intermediate layer (C-d) and the outermost layer polymer (C-c) on the crosslinked rubber elastic body, Here, the gel content means that a 1% by weight MEK solution of a multilayer structure polymer is prepared, left standing at 25 ° C. for one day and then centrifuged, and then, at 16000 r.p.m. p. m. It is the weight% of the insoluble matter after centrifugation for 90 minutes. The component is the additional weight of the two-layer crosslinked rubber elastic body and the graft layer, and it can be replaced by the graft ratio, but since it has a special structure in the present invention, the gel content is used as a guide for the graft amount.

When carrying out the present invention, it is important to keep the amount of metal remaining in the final product at 500 ppm or less when salting out with a metal salt. Is one.

As the method for producing the multi-layer structure polymer (C) 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. It can be carried out by emulsion suspension polymerization in which the outer layer polymer (C-c) is converted into a suspension polymerization system during polymerization.

Next, the composition and production method of the polymer (D) will be described.

The polymer (D) is a thermoplastic polymer (D-1).
0.1 to 20% by weight, rubber-containing polymer (D-2) 5 to 8
0% by weight, and the total of 0 to 93.9 parts by weight of the thermoplastic polymer (D-3) is 100% by weight. In the following (D-
Each of the polymers 1) to (D-3) will be described.

The thermoplastic polymer (D) in the polymer (D) component
-1) is at least one other vinyl monomer 0 to 50 copolymerizable with 50 to 100% by weight of methyl methacrylate.
And the reduced viscosity of the polymer (polymer 0.1 g
Is a polymer which is dissolved in 100 ml of chloroform and is measured at 25 ° C.) to exceed 0.1 L / g, and is a component which plays an important role for film moldability. Thermoplastic polymer (D
The reduced viscosity of -1) is important, and the reduced viscosity is 0.1 L /
If it is g or less, a film with good thickness accuracy cannot be obtained. The reduced viscosity is usually more than 0.1 L / g and 2 L / g or less, preferably 0.2 to 1.2 L / g.

In the thermoplastic polymer (D-1), an acrylic acid alkyl ester, a methacrylic acid alkyl ester, an aromatic vinyl compound or a vinyl cyan compound is used as the vinyl monomer which can be polymerized together with methyl methacrylate. You can

The production of the thermoplastic polymer (D-1) is preferably carried out by an emulsion polymerization method, and can be recovered in powder form by a usual emulsion polymerization method and post-treatment method.

The rubber-containing polymer (D-2) has a function of imparting excellent impact resistance and elongation to the resin composition and has a multi-layered graft copolymer containing an alkyl acrylate as a main rubber component. It is a polymer. Further, it is a component necessary for exhibiting a good matting property. Rubber-containing polymer (D-2)
Is a single amount consisting of 50 to 99.9% by weight of alkyl acrylate, 0 to 40% by weight of another copolymerizable vinyl monomer, and 0.1 to 10% by weight of a copolymerizable crosslinkable monomer. Monomer consisting of 50 to 100% by weight of methacrylic acid ester in the presence of 100 parts by weight of an elastic copolymer obtained by polymerizing a body mixture and 0 to 50% by weight of a vinyl monomer copolymerizable therewith. It is obtained by polymerizing 10 to 2000 parts by weight of a body or a mixture thereof in at least one step.

The alkyl acrylate used herein has 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 vinyl monomer used here, 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, trimethylol 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.

The rubber-containing polymer (D-2) in the present invention is
Obtained by ordinary 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-containing polymer (D
-2) is used in the range of 5 to 80% by weight in the polymer (D), but it is preferably 30% by weight, more preferably 50% by weight or more in order to develop the matting property.

The thermoplastic polymer (D-
3) is 50 to 99.9% by weight of a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms, 0.1 to 50% by weight of an acrylic acid ester having an alkyl group of 1 to 8 carbon atoms, and It comprises 0 to 49.9% by weight of at least one other copolymerizable vinyl monomer, and has a reduced viscosity of the polymer (measured at 25 ° C. by dissolving 0.1 g of the polymer in 100 ml of chloroform). It is a polymer of not more than 1 L / g.

As the methacrylic acid ester used in the thermoplastic polymer (D-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 (D-3) is as follows:
Although not particularly limited, ordinary suspension polymerization, emulsion polymerization, bulk polymerization and the like can be used for 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.

Next, a composition suitable for obtaining the linear polymer (B) having a hydroxyl group used in the present invention will be shown.

Acrylic acid hydroxyalkyl ester,
Or / and methacrylic acid hydroxyalkyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate,
4-hydroxybutyl acrylate and the like are included. Among these, 2-hydroxyethyl methacrylate is particularly preferable.

Acrylic acid hydroxyalkyl ester,
Alternatively, and / or the amount of the methacrylic acid hydroxyalkyl ester 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, if it exceeds 80% by weight, the elongation may decrease or the surface condition may become poor. The preferred range of use for expressing matte properties is 5 to
It is 50% by weight. More preferably, it is desirable to use in the range of 20 to 50% by weight.

As the methacrylic acid alkyl ester,
Lower methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate are preferred, and methyl methacrylate is particularly preferred. The amount of the methacrylic acid alkyl ester used is required to be in the range of 10 to 99% by weight. Preferably 30-85% by weight
It is desirable to use within the range.

79% by weight of alkyl acrylate
Can be used in a range of up to, specifically methyl acrylate,
Ethyl acrylate, butyl acrylate, acrylic acid 2-
Lower acrylic acid alkyl esters such as ethylhexyl are preferred. Acrylic acid alkyl ester is 0.5-4
It is desirable to use it in the range of 0% by weight. More preferably, it is 5 to 25% by weight.

Furthermore, in the linear polymer (B) of the present invention, at least one other vinyl monomer may be used within the range 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.

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 generally used are used, and examples thereof include organic colloidal polymeric substances, inorganic colloidal polymeric substances, inorganic fine particles, and combinations of these with a surfactant.

It is possible to use a polymerization degree controlling agent such as mercaptan, and it is rather preferable to control the molecular weight distribution using them.

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 4 with respect to 100 parts by weight of the acrylic resin (A).
It is in the range of 0 parts by weight. In order to obtain a good matting property, it is preferable to use 2.0 parts by weight or more.

One of the features of the present invention is that when (C) and (D) are used as the acrylic resin, the haze value is improved. When the acrylic resin is used as a film, it may be laminated on a vinyl chloride resin for the purpose of improving weather resistance. In this case, the pattern printed on the vinyl chloride resin must be clearly visible, and it is desirable that the acrylic resin film has a low haze value. It is preferable that the haze value is 10% or less when a film having a thickness of 50 μ is applied and soapy water is applied to smooth the surface.

As a method for mixing the resin composition of the present invention,
Suitable methods such as passing through a screw type extruder in which the mixture is simultaneously shear-compressed, kneading between heating rolls, and mixing in a heating high shear mixing device such as a Burberry type mixer are generally used.

The resin composition of the present invention may optionally contain a general compounding agent such as a stabilizer, a lubricant, a processing aid, an impact resistance aid,
It may contain plasticizers, foaming agents, fillers, colorants and the like. The resin composition of the present invention thus obtained can be easily molded into a film, sheet or the like by a conventional method such as a T-die method, an inflation method, a calender method, an extrusion molding method or the like. Further, it is possible to produce a thermoplastic resin laminate having a thermoplastic resin composition in the surface layer and having excellent matting properties. As the base material on which the thermoplastic resin composition is laminated, known thermoplastic resins can be used, but acrylic resins, polycarbonate resins, vinyl chloride resins and ABS resins are preferred.

As a method for producing a thermoplastic resin laminate using a thermoplastic resin composition having excellent matting properties, one film is formed and then a solution containing another polymer is cast to remove the solvent. A known lamination method can be adopted without particular limitation, such as a method of performing the above, but a coextrusion method using an extruder, an extrusion lamination method, and a thermal lamination method using a heating roll are preferable.

In the thermoplastic resin laminate of the present invention, an intermediate layer can be provided between the thermoplastic resin composition of the surface layer and the thermoplastic resin of the base material.

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

[0060]

The present invention will be described in more detail with reference to the following examples. In addition, all the numbers of parts in the following examples are based on weight.

The evaluation methods used in the examples are as follows.

(1) The 60 degree surface glossiness was evaluated by a gloss meter GM-26D manufactured by Murakami Color Research Laboratory.

(2) Surface condition: The surface condition (roughness, uniformity) was visually evaluated as a standard for evaluating the dispersibility.

◯: Very good Δ: Normal ×: Poor (3) Haze value was measured by applying soap water to the surface of the film using a haze meter SEP-H-SS manufactured by Nippon Seimitsu Optical Co., Ltd. .

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

Methyl acrylate 20 parts Methyl methacrylate 60 parts 2-Hydroxyethyl methacrylate 20 parts t-Dodecyl mercaptan 0.5 parts Lauroyl peroxide 1 part Tricalcium phosphate 5 parts Water 250 parts Sufficient nitrogen gas in the container After the substitution, 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 linear polymer (B).

(2) Production of multi-layer structure polymer (C) A polymerization vessel equipped with a condenser was charged with 250 parts of ion-exchanged water, 2 parts of ester soda salt of sulphosuccinic acid, and 0.05 part of sodium formaldehyde sulfoxylate. ,
After stirring under nitrogen, 1.6 parts of methyl methacrylate, 8 parts of butyl acrylate, 0.4 parts of 1,3 butylene glycol dimethacrylate, 0.1 parts of allyl methacrylate.
Parts and 0.04 parts of cumene hydroperoxide. After the temperature is raised to 70 ° C., the reaction is continued for 60 minutes to complete the polymerization of the innermost layer polymer (Ca).
Subsequently, 1.5 parts of methyl methacrylate and butyl acrylate 22.5 forming a crosslinked elastic polymer (Cb).
Part, 1,3 butylene glycol dimethacrylate 1.
A mixture of 0 part, 0.25 part of allyl methacrylate and 0.05 part of cumene hydroperoxide was added over 60 minutes and polymerized 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 each was 1
It was 0% and 90%.

Subsequently, a mixture of 5 parts of methyl methacrylate, 5 parts of butyl acrylate and 0.1 part of allyl methacrylate was reacted as the intermediate layer (C-d), and finally methyl methacrylate was used as the outermost layer polymer (C-c).
Polymerization was completed by reacting a mixture having a composition of 52.25 parts and 2.75 parts of butyl acrylate. The obtained polymer emulsion was salted out with 5 parts of calcium chloride based on 100 parts of the polymer, washed, and dried to obtain a multilayer structure polymer (C).

The residual amount of calcium in the final polymer composition was approximately 200 ppm. (3) Manufacture of Matting Thermoplastic Resin Composition 100 parts of the multi-layered polymer obtained in Example 1 (2) was added to the linear polymer (B) obtained in Example 1 (1). ) Was mixed and mixed, and the mixture was extruded and cut at 240 ° C. to be pelletized by a twin-screw extruder. The obtained pellets were dried and formed into a film having a thickness of about 50 μm at 240 ° C. by a T-die method, and the 60 ° surface glossiness, the surface state of the film, and the haze value were evaluated. The results are shown in Table 1.

[0071]

[Table 1]

Examples 2 to 8 Example 1 except that the composition of the linear polymer (B) and the blending amount in the multilayer structure polymer (C) were changed as shown in Table 1.
The experiment was conducted in the same manner as (3). The results are also shown in Table 1.

Example 9 (Production of a thermoplastic resin laminate having excellent matting properties) 100 parts of the multilayer structure polymer obtained in Example 1 (2) was obtained in Example 1 (1). 10 parts of the above linear polymer was mixed and mixed, and the mixture was extruded and cut into pellets at 240 ° C. by a twin-screw extruder. After drying the obtained pellets, acrylic resin pellets (Acrypet V manufactured by Mitsubishi Rayon Co., Ltd.)
H) together with the coextrusion method so that the matte thermoplastic resin layer has a thickness of 100 μ and the acrylic resin layer has a thickness of 2 mm.
Molding was carried out at 40 ° C. to obtain a thermoplastic resin laminate having excellent matting properties. The 60 degree surface glossiness and the surface condition of the film were evaluated. The results are shown in Table 2.

[0074]

[Table 2]

Example 10 The same as Example 9 except that the thermoplastic resin on which the matte thermoplastic resin composition was laminated was changed to a polycarbonate resin (GE Plastic Lexan ML-5500) and molding was performed at 280 ° C. The experiment was conducted. The results are also shown in Table 2.

Example 11 100 parts of a vinyl chloride resin (P = 720), 3 parts of a stabilizer (dibutyltin maleate), an impact resistance additive (Mitsubishi Corporation) were used as the thermoplastic resin on which the matte thermoplastic resin composition was laminated. Except for changing to a hard vinyl chloride resin consisting of 10 parts of rayon, Metabrene C-102), 1 part of processing aid (Mitsubishi Rayon, Metabrene P-551), 1 part of lubricant (butyl stearate), and molding at 200 ° C. The experiment was performed in the same manner as in Example 9. The results are also shown in Table 2.

Example 12 A thermoplastic resin laminated with a matte thermoplastic resin composition was made of ABS resin (Diapet ABS manufactured by Mitsubishi Rayon Co., Ltd.).
The experiment was performed in the same manner as in Example 9 except that the temperature was changed to 3001M) and the molding was performed at 240 ° C. The results are also shown in Table 2.

Example 13 An experiment was carried out in the same manner as in Example 9 except that the method for producing a thermoplastic laminate having excellent matte properties was changed to the extrusion lamination method. Specifically, with respect to 100 parts of the multilayer structure polymer obtained in Example 1 (2), 10 parts of the linear polymer obtained in Example 1 (1) was blended and mixed to obtain biaxial. 24 in the extruder
It was extruded at 0 ° C. and cut into pellets. After drying the obtained pellets, a film having a thickness of about 50 μm was obtained by T-die method at 240 ° C. Next, when the acrylic resin (Acrype VH) was extrusion molded at 240 ° C. to form a 2 mm sheet, extrusion lamination was performed by introducing the above-mentioned film between the molten acrylic resin and the cooling roll. The results are also shown in Table 2.

Example 14 An experiment was conducted in the same manner as in Example 9 except that the method for producing a thermoplastic laminate having excellent matte properties was changed to the thermal lamination method. Specifically, the film obtained in Example 1 (3) was subjected to heat lamination 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 . The results are also shown in Table 2.

Example 15 (1) Production of linear polymer (B) A mixture of 10 parts of methyl acrylate, methyl methacrylate and various hydroxyalkyl methacrylates in a ratio shown in Table 2 was added to n-octyl. 0.35 part of mercaptan was dissolved, and lauroyl peroxide as a polymerization catalyst was added in an amount of 0.
35 parts, copolymer of methyl methacrylate and sulfoethyl methacrylate sodium salt as a suspension polymerization dispersant 0.0
2 parts, 0.35 parts of sodium sulfate, and 145 parts of ion-exchanged water as a dispersion medium were mixed in a reaction vessel, polymerized at 70 ° C., and after keeping the internal temperature at a peak, it was kept at 95 ° C. for 30 minutes, cooled, filtered, It was washed with water and dried to obtain a linear polymer (B) having a hydroxyl group.

(2) Production of thermoplastic polymer (D-1) 200 parts of ion-exchanged water whose atmosphere was replaced with nitrogen were charged into a reaction vessel, 1 part of an emulsifier potassium oleate and 0.3 part of potassium persulfate were charged. Subsequently, 40 parts of methyl methacrylate, 10 parts of n-butyl acrylate and 0.0 parts of n-octyl mercaptan.
05 parts were charged and the mixture was stirred at 65 ° C. for 3 hours under a nitrogen atmosphere to complete the polymerization. Followed by methyl methacrylate 48
Part, and a monomer mixture consisting of 2 parts of n-butyl acrylate were added dropwise over 2 hours, and after completion of the addition, the mixture was held for 2 hours to complete the polymerization. The obtained latex was added to a 0.25% sulfuric acid aqueous solution, and the polymer was acid-deposited, dehydrated, washed with water and dried to recover the polymer in a powder form. Reduced viscosity η of the obtained polymer
The sp / c was 0.38 L / g.

(3) Production of Rubber-Containing Polymer (D-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 Styrene 22.7 parts Allyl methacrylate 0.3 parts Sodium dioctyl sulfosuccinate 2.0 parts Deionized water 300 parts Potassium persulfate 0.3 parts Disodium phosphate dodecahydrate 0.5 parts Sodium hydrogen phosphate dihydrate 0.3 part 100 parts by weight (as solid content) of this elastic latex are placed in a reaction vessel, and the atmosphere is sufficiently replaced with nitrogen.
After heating to 0 ° C., an aqueous solution containing 0.125 parts of sodium formaldehyde sulfoxylate and 2 parts of deionized water was added, and then while maintaining the temperature at 80 ° C., 60 parts of methyl methacrylate, 0.05 part of n-octyl mercaptan. , T-butyl hydroperoxide (0.125 parts) was added dropwise over 2 hours, and the mixture was maintained 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.

(4) Manufacture of thermoplastic resin composition having excellent matting properties As described above, the linear polymers (B) and (2) obtained in Example 15 (1) were obtained. Thermoplastic polymer (D-
1), the rubber-containing polymer (D-2) obtained in (3) and the thermoplastic polymer (D-3) methyl methacrylate / methyl acrylate copolymer (methyl methacrylate / methyl acrylate = 90/10, ηsp / c = 0.051L /
g) was mixed with a Henschel mixer in the proportions shown in Table 4. Next, 40 mmφ screw type extruder (L / D =
26) was melt-kneaded at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C., and pelletized. The obtained pellets were dried and then extrusion-molded under the following conditions to obtain a film.

40 mmφ (screw diameter) extruder with 300 mm T die Resin temperature 245 ° C. Discharge rate 15 kg / hour (for thickness 20 μm) Moldability, glossiness, and film appearance of the obtained film are shown in Table 4.

Examples 16 to 29 Polymerization monomer composition as shown in Table 3, and linear polymer (B) and each polymer (D-1) to (D- as shown in Table 4
An experiment was conducted in the same manner as in Example 15 (4) except that the addition amount of 3) was changed. The results are shown in Table 4.

[0087]

[Table 3]

[0088]

[Table 4]

Example 30 (Production of thermoplastic resin laminate having excellent matting properties) 100 parts of the polymer (D) obtained in Example 15 was used.
10 parts of the linear polymer (B) obtained in Example 17 was blended and mixed, and the mixture was extruded and cut at 240 ° C. with a twin-screw extruder to be pelletized. After drying the obtained pellets, acrylic resin pellets (Mitsubishi Rayon Acrypet VH)
Together with the coextrusion molding method, the matte thermoplastic resin (I)
So that the layer is 100μ and the acrylic resin layer is 2mm,
Molding was performed at 240 ° C. to obtain a thermoplastic resin laminate having excellent matting properties. The 60 degree surface glossiness and the surface condition of the film were evaluated. The results are shown in Table 5.

[0090]

[Table 5]

Example 31 Same as Example 30 except that the thermoplastic resin on which the matte thermoplastic resin composition was laminated was changed to a polycarbonate resin (GE Plastic Lexan ML-5500) and molding was performed at 280 ° C. The experiment was conducted. The results are also shown in Table 5.

Example 32 100 parts of a vinyl chloride resin (P = 720), 3 parts of a stabilizer (dibutyltin maleate), and an impact resistance auxiliary agent (Mitsubishi Corporation) were used as the thermoplastic resin laminated with the matte thermoplastic resin composition. Except for changing to a hard vinyl chloride resin consisting of 10 parts of rayon, Metabrene C-102), 1 part of processing aid (Mitsubishi Rayon, Metabrene P-551), 1 part of lubricant (butyl stearate), and molding at 200 ° C. The experiment was conducted in the same manner as in Example 30. The results are also shown in Table 5.

Example 33 A thermoplastic resin laminated with a matte thermoplastic resin composition was prepared from ABS resin (Diapet ABS manufactured by Mitsubishi Rayon Co., Ltd.).
The experiment was performed in the same manner as in Example 30 except that the temperature was changed to 3001M) and the molding was performed at 240 ° C. The results are also shown in Table 5.

Example 34 An experiment was carried out in the same manner as in Example 30 except that the extrusion lamination method was used instead of the method for producing a thermoplastic laminate having excellent matte properties. Specifically, the polymer (D) obtained in Example 15
To 100 parts, 10 parts of the linear polymer obtained in Example 17 was blended and mixed, and the mixture was extruded and cut at 240 ° C. into a pellet by a twin-screw extruder. After drying the obtained pellets, a film having a thickness of about 50 μm was obtained by T-die method at 240 ° C. Next, when the acrylic resin (Acrype VH) was extrusion molded at 240 ° C. to form a 2 mm sheet, extrusion lamination was performed by introducing the above-mentioned film between the molten acrylic resin and the cooling roll. The results are also shown in Table 5.

Example 35 An experiment was carried out in the same manner as in Example 17 except that the method for producing a thermoplastic laminate having excellent matteness was changed to the thermal lamination method. Specifically, the film obtained in Example 17 was heat-laminated with a 100 μm-thick soft vinyl chloride film at 150 ° C. and 30 kg / cm ² using an embossing laminating roll. The results are also shown in Table 5.

Comparative Example 1 Only the multilayer structure polymer obtained in Example 1 (2) was formed into a film having a thickness of about 50 μm in the same manner as in Example 1 (3), and its 60 ° surface gloss was measured. The surface condition of the film was evaluated and is shown in Table 1. From this comparative example, it can be seen that no matting property is exhibited unless the linear polymer (B) is used.

Comparative Example 2 10 parts of a crosslinkable matting agent (Mitsubishi Rayon Metabrene F410) was added to the multilayer structure polymer obtained in Example 1 (2), and a film was formed in the same manner as in Example 1 (3). Then, a film having a thickness of about 50 μ was prepared, and its 60 degree surface glossiness and the surface condition of the film were evaluated and shown in Table 1. From this comparative example, it is understood that the matting property is improved by the copolymerization of hydroxyalkyl (meth) acrylate without impairing the surface condition.

Comparative Examples 3 to 5 Experiments were carried out in the same manner as in Example 1 except that the composition of the linear polymer (B) was changed as shown in Table 1. The results are also shown in Table 1. From the results of the comparative examples, it is understood that the monomer composition is important for the linear polymer (B) used in the present invention.

Comparative Example 6 An experiment was carried out in the same manner as in Example 15 (4) except that a crosslinkable matting agent (Mitsubishi Rayon Metabrene F410) was used instead of the linear polymer (B). The results are shown in Table 4.
This comparative example shows that the use of the linear polymer (B) improves the matteness and / or appearance.

Comparative Example 7 Example 15 (4) except that the copolymer (B) was not used.
An experiment was conducted in the same manner as. The results are shown in Table 4. From this comparative example, it can be seen that the matting property is not exhibited unless the linear polymer (B) is used.

Comparative Example 8 An experiment was conducted in the same manner as in Example 15 (4) except that the thermoplastic polymer (D-1) was not used. The results are shown in Table 4.
This comparative example shows that a good film cannot be obtained unless the thermoplastic polymer (D-1) is used.

Comparative Example 9 As shown in Table 3, film formation was carried out in the same manner as in Example 15 (4) except that 85% by weight of hydroxyalkyl (meth) acrylate in the linear polymer (B) was used. It was The results are shown in Table 4. This comparative example shows that a good film cannot be obtained when the amount of hydroxyalkyl (meth) acrylate in the linear polymer (B) exceeds 80% by weight.

[0103]

EFFECT OF THE INVENTION A laminate comprising a thermoplastic resin composition of the present invention and a film-like product obtained from the thermoplastic resin composition in a surface layer is a conventional glossy film without impairing the surface condition. The matting properties and / or the external appearance, which were insufficient when the desensitizer was used, were greatly improved, so that an industrially excellent effect was exhibited.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroki Hatakeyama 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Otake Office

Claims (2)

[Claims] 1. Acrylic resin (A) 100 parts by weight and 1 to 80% by weight of hydroxyalkyl acrylate or hydroxyalkyl methacrylate (b-1) having an alkyl group having 1 to 8 carbon atoms and 1 carbon atom. ~ 13
Methacrylic acid alkyl ester (b-2) having 10 to 99% by weight and acrylic acid alkyl ester (b-3) 0 having alkyl group having 1 to 8 carbon atoms
A thermoplastic resin composition comprising 1 to 40 parts by weight of a linear polymer (B) having a hydroxyl group, which is comprised from 0 to 79% by weight and from 0 to 50% by weight of at least one other copolymerizable vinyl monomer. 2. A laminate comprising a film-like material obtained from the thermoplastic resin composition according to claim 1 as a surface layer.