JPH07314615A - Thermoplastic resin laminate - Google Patents

Abstract

PURPOSE:To improve the matting properties and obtain industrially excellent effect by forming a matting resin compsn. prepared by compounding a specific amt. of a crosslinked polymer obtained by polymerizing a specific mixture on a surface layer. CONSTITUTION:A specific matting thermoplastic resin compsn. is formed on at least a surface. This matting thermoplastic resin compsn. is prepared by compounding 0.1-40 pts.wt. of crosslinked polymer obtained by polymerizing a mixture consisting of 0.5-80wt.% of hydroxyl alkyl (meth)acrylate, 10-99wt.% of alkyl methacrylate, 0-79wt.% of alkyl acrylate, 0-70wt.% of a vinyl aromatic monomer, 90-below 100wt.% of a non-crosslinkable monomer mixture containing 0-20wt.% of a monoethylenic unsaturated monomer and 0-5wt.% of a crosslinkable monomer having a double bond in its molecule with 100 pts.wt. of a thermoplastic resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin laminate excellent in mattness.

[0002]

2. Description of the Related Art Acrylic resin, polycarbonate resin,
Molded articles obtained from thermoplastic resins such as vinyl chloride resin and ABS resin generally have luster, which may be an important characteristic depending on the application. On the other hand, on the other hand, there are many applications in which such luster is not necessary, or rather, luster is preferred.

[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 in physical properties, but has poor productivity and a high processing cost, and the matting effect is insufficient. In many cases, it is not suitable for secondary processing. . On the contrary, the method (2) can control the degree of matting without lowering the productivity so much 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 using the above-mentioned high molecular weight matting agent, the physical properties such as impact resistance and strength / elongation are less deteriorated, but the matting effect is insufficient. . The present invention aims to solve these problems.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a crosslinked polymer obtained from (meth) acrylic acid hydroxyalkyl ester, methacrylic acid alkylester and a specific crosslinkable monomer is thermoplastic. The present invention was achieved by solving the above problems by laminating a thermoplastic resin composition blended with a resin on the surface of the thermoplastic resin.

That is, the gist of the present invention is that the carbon number of the alkyl group is 1 to 100 parts by weight of the thermoplastic resin (A).
8 (meth) acrylic acid hydroxyalkyl ester (b-1) 0.5 to 80% by weight, alkyl group having 1 carbon atom
Methacrylic acid alkyl ester (b-2) 10
To 99 wt%, 0 to 79 wt% acrylic acid alkyl ester (b-3) having 1 to 8 carbon atoms of an alkyl group, 0 to 70 wt% vinyl aromatic monomer (b-4), and other monoethylenic Non-crosslinkable monomer mixture (B-1) 95-1 consisting of 0-20% by weight of saturated monomer (b-5)
Less than 00% by weight and more than 0% by weight to 5% by weight of a crosslinkable monomer (B-2) having two or more double bonds in the molecule.
Characterized in that it has a matte thermoplastic resin composition (I) formed by blending 0.1 to 40 parts by weight of a crosslinked polymer (B) obtained by polymerizing a mixture of It is in a thermoplastic resin laminate.

Examples of the thermoplastic resin (A) used in the present invention include acrylic resin, vinyl chloride resin, ABS resin and the like, among which acrylic resin is most preferable.
The crosslinked polymer (B) in the present invention is obtained from the non-crosslinkable monomer mixture (B-1) and the crosslinkable monomer (B-2).

The non-crosslinkable monomer mixture (B-1) used in the present invention comprises an alkyl group (meth) having 1 to 8 carbon atoms.
Acrylic acid hydroxyalkyl ester (b-1) 0.
5 to 80% by weight, alkyl group having 1 to 13 carbon atoms of methacrylic acid alkyl ester (b-2) 10 to 99% by weight,
Acrylic acid alkyl ester having 1 to 8 carbon atoms of alkyl group (b-3) 0 to 79% by weight, vinyl aromatic monomer (b-4) 0 to 70% by weight, other monoethylenically unsaturated monomer (b- 5) 0 to 20% by weight.

Examples of the (meth) acrylic acid hydroxyalkyl ester (b-1) having an alkyl group having 1 to 8 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 2,3-dihydroxypropyl methacrylate. , 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and the like,
2-Hydroxyethyl methacrylate is particularly preferable.

The (meth) acrylic acid hydroxyalkyl ester having 1 to 8 carbon atoms in the alkyl group can be used in the range of 0.5 to 80% by weight in the non-crosslinking monomer mixture, and further 1 to 40% by weight. It is preferable to use in the range of. If it is less than 0.5% by weight, the matting effect is insufficient, while if it exceeds 80% by weight, the surface condition of the obtained molded article tends to be poor.

Methacrylic acid alkyl ester (b-2)
As, methyl methacrylate, ethyl methacrylate,
Examples thereof include lower methacrylic acid alkyl esters such as butyl methacrylate, with methyl methacrylate being preferred. The methacrylic acid alkyl ester is contained in the non-crosslinkable monomer mixture in an amount of 10 to 10 in terms of the surface appearance of the obtained molded product.
Used in the range of 99% by weight. Preferably 15-70
Used in the weight% range.

Examples of the alkyl acrylate (b-3) include lower acrylic acid alkyl esters such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, with butyl acrylate being preferred.
The alkyl acrylate can be used in the range of up to 79% by weight in the non-crosslinkable monomer mixture. Preferably 0.5-40% by weight, more preferably 5-25% by weight
Is.

As the vinyl aromatic monomer (b-4), styrene, vinyltoluene, α-methylstyrene,
Halogenated styrene and the like can be mentioned, but styrene is particularly preferable. The vinyl aromatic monomer can be used in the range of up to 70% by weight in the non-crosslinkable monomer mixture. It is preferably 10 to 60% by weight, more preferably 15 to 55% by weight.

Monoethylenically unsaturated monomer (b-5)
Known monomers can be used as, for example, methacrylic acid, fumaric acid, maleic acid, and copolymerizable carboxylic acids and their esters, which have 1 carbon atom in the alkyl group.
To 13 methacrylic acid alkyl esters, those excluding alkyl acrylates having 1 to 8 carbon atoms in the alkyl group, vinyl halides such as vinyl chloride and vinyl bromide, vinyl esters such as vinyl acetate, and acrylonitrile. . Monoethylenically unsaturated monomers can be used in the range of up to 20% by weight in the non-crosslinkable monomer mixture. It is preferably 10% by weight.

As the crosslinkable monomer (B-2), a compound having two or more unsaturated bonds in the molecule is used. Specifically, allyl group-containing crosslinkable monomers such as allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate, unsaturated carboxylic acid esters of alkylene glycol such as ethylene glycol dimethacrylate, and alkylene glycol such as propylene glycol diallyl ether. Examples include saturated alcohol ethers and polyvalent vinylbenzenes such as divinylbenzene.

Particularly preferred is a compound in which at least one of the two or more unsaturated bonds is an allyl group. By using the above-mentioned allyl group-containing crosslinkable monomer, it becomes possible to provide the crosslinked polymer with a proper crosslink composition distribution. Of these, allyl methacrylate is particularly preferable. The amount of the crosslinkable monomer added is in the mixture of the noncrosslinkable monomer and the crosslinkable monomer,
More than 0% by weight and up to 5% by weight. If the cross-linking monomer is not added, the matting property may not be sufficient, and if it exceeds 5% by weight, the surface condition may be deteriorated.

The crosslinked polymer (B) of the present invention can be produced by a usual polymerization method, but it is particularly preferably obtained by suspension polymerization.

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 a surfactant.

It is possible to use a polymerization degree controlling agent such as mercaptan, and it is often 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. Other than that, use a polymer that is soluble in the monomer by dissolving it in the monomer, or after partially polymerizing in bulk without adding the crosslinkable monomer, add the crosslinkable monomer or suspension stabilizer, etc. You can also

The particle size of the crosslinked polymer produced is preferably 5 to 500 μm, more preferably 40 to 250 μm. If the average particle size is less than 5 μ, the matteness is not sufficient, and conversely, if it exceeds 500 μm, the surface of the obtained molded product becomes rough and it is difficult to obtain a uniform matte, which is not preferable.

The amount of the crosslinked polymer (B) compounded is in the range of 0.1 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), and 1 part by weight or more is used from the viewpoint of matting effect. Is preferable, and it is more preferable to use 3 parts by weight or more.

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

The matte thermoplastic resin composition (I) is a general compounding agent, if necessary, such as a stabilizer, a lubricant, a processing aid, an impact resistance aid, a plasticizer, a foaming agent, a filler and a colorant. Can be included.

The matte thermoplastic resin composition (I) is laminated in the form of a film or sheet on a thermoplastic resin such as an acrylic resin, a polycarbonate resin, a vinyl chloride resin or an ABS resin to form the thermoplastic resin of the present invention. It is a resin laminate.
In particular, acrylic resin and polycarbonate resin are preferable.

The method for producing the thermoplastic resin laminate of the present invention includes, in addition to coextrusion molding using an extruder, extrusion lamination molding and thermal lamination, other polymer after forming one film. A known lamination method can be adopted without particular limitation, such as a method of casting a solution to remove the solvent.

Further, the laminate may have an intermediate layer between the surface layer and the thermoplastic resin.

Further, this laminate can be easily printed and its design effect can be remarkably enhanced.

[0031]

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

The evaluation methods used in the examples are as follows.

(1) The 60-degree specular gloss was measured using 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 Example 1 (1) Production of crosslinked 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. .

Styrene 30 parts Butyl acrylate 20 parts Methyl methacrylate 30 parts 2-Hydroxyethyl methacrylate 20 parts Allyl methacrylate 2 parts t-Dodecyl mercaptan 0.5 parts Lauroyl peroxide 1 part Tricalcium phosphate 20 parts Water 250 parts Container After sufficiently replacing the inside 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 crosslinked polymer beads. The particle size of the produced beads is 5-500μ
The weight average particle diameter was around 100 μm. The beads obtained had the following particle size distribution.

Mesh weight% 32 or more 1.0 32 to 48 2.4 48 to 100 13.3 100 to 150 57.1 150 to 200 15.1 200 to 250 7.6 250 to 400 3.2 400 or less 0 .3 (2) Manufacture of matte thermoplastic resin laminate The crosslinked polymer obtained in Example 1 (1) was used as a resin for MMA film (manufactured by Mitsubishi Rayon Co., Ltd., Hipet HBS0).
01) 8 parts per 100 parts were mixed and mixed, and extruded and cut at 240 ° C. with a twin-screw extruder to form pellets. After drying the obtained pellets, a matte thermoplastic resin (I) layer of 100 μ was formed by a coextrusion molding method together with an acrylic resin pellet (Acrypet VH manufactured by Mitsubishi Rayon Co., Ltd.).
Molding was performed at 240 ° C. so that the acrylic resin layer had a thickness of 2 mm to obtain a thermoplastic resin laminate. The 60-degree specular gloss and the surface condition of the laminate were evaluated. The results are shown in Table 1.

[0038]

[Table 1]

Examples 2 to 8 Experiments were carried out in the same manner as in Example 1 except that the composition of the crosslinked polymer (B) and the amount of the resin for MMA film were changed as shown in Table 1. The results are shown in Table 1.

Example 9 Example except that the thermoplastic resin on which the matte thermoplastic resin composition (I) was laminated was changed to polycarbonate resin (GE Plastic Lexan ML-5500) and molding was performed at 280 ° C. The experiment was performed in the same manner as 1. The results are shown in Table 1.
Shown in.

Example 10 100 parts of a vinyl chloride resin (P = 720), 3 parts of a stabilizer (dibutyl tin maleate), an impact resistance auxiliary agent (Mitsubishi Change to a hard vinyl chloride resin composition 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 at 200 ° C. Example 1 except for molding
I went the same way. The results are shown in Table 1.

Example 11 The thermoplastic resin laminated with the matte thermoplastic resin composition was ABS resin (Diapet ABS manufactured by Mitsubishi Rayon Co., Ltd.).
The same procedure as in Example 1 was performed except that the temperature was changed to 3001M) and the molding was performed at 240 ° C. The results are shown in Table 1.

Example 12 An experiment was conducted in the same manner as in Example 1 except that the method for producing the laminate was changed to the extrusion lamination method. Specifically, MMA
Resin for film (HI-PET H manufactured by Mitsubishi Rayon Co., Ltd.)
8 parts of the crosslinked polymer (B) obtained in Example 1 (1) was mixed and mixed with 100 parts of BS001), and the mixture was extruded and cut at 240 ° C. with a twin-screw extruder to be pelletized. 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 (Acrypet VH manufactured by Mitsubishi Rayon) is extrusion-molded at 240 ° C. to form a 2 mm sheet, by introducing the above-mentioned film between the molten acrylic resin and the cooling roll, extrusion lamination can be achieved. went. The results are shown in Table 1.

Example 13 An experiment was conducted in the same manner as in Example 1 except that the method for producing a laminate was changed to the thermal lamination method. Specifically, Example 1
Using the laminating roll with embossing, the film obtained in 2 and 15
Thermal lamination was performed under the conditions of 0 ° C. and 30 kg / cm 2. The results are shown in Table 1.

Comparative Example 1 Instead of the crosslinked polymer (B), 8 parts of a crosslinkable matting agent (Mitsubishi Rayon Metablen F410) was blended, and the same experiment as in Example 1 was conducted. The results are shown in Table 2.

Comparative Example 2 Molding was carried out in the same manner as in Example 1 without using the crosslinked polymer (B), the 60-degree specular gloss and the surface condition of the laminate were evaluated, and the results are shown in Table 1.

Comparative Example 3 An experiment was conducted in the same manner as in Example 1 except that the composition of the crosslinked polymer (B) was changed as shown in Table 1. The results are shown in Table 1.

[0048]

INDUSTRIAL APPLICABILITY The thermoplastic resin laminate of the present invention greatly improves the mattness which was insufficient when the conventional matting agent was used, without impairing the surface condition, and thus is industrially useful. It has an excellent effect.

Claims (1)

[Claims] 1. A thermoplastic resin laminate comprising a matte thermoplastic resin composition (I) shown below in at least a surface layer. Matting thermoplastic resin composition (I) 0.5- (meth) acrylic acid hydroxyalkyl ester (b-1) having 1 to 8 carbon atoms of an alkyl group based on 100 parts by weight of the thermoplastic resin (A). 80% by weight, alkyl methacrylate having 1 to 13 carbon atoms (b)
-2) 10 to 99% by weight, 0 to 79% by weight of an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group (b-3), 0 to 70% by weight of a vinyl aromatic monomer (b-4) and other Monoethylenically unsaturated monomer (b-5)
Non-crosslinkable monomer mixture (B-
1) Obtained by polymerizing a mixture consisting of 95 to less than 100% by weight and more than 0 to 5% by weight of a crosslinkable monomer (B-2) having two or more double bonds in the molecule. A matte thermoplastic resin composition comprising 0.1 to 40 parts by weight of a crosslinked polymer (B).