JPH0673200A - Delustered film for laminate - Google Patents

Abstract

PURPOSE:To provide the subject product composed of a resin mixture having a specified composition, excellent in delustering properties after lamination and suitable as a protective film of a furniture, etc., for which a delustered film is preferably used. CONSTITUTION:The objective product is composed of a resin mixture obtained by blending (A) a thermoplastic polymer composed of 50 to 100wt.% methyl methacrylate and 0 to 50wt.% vinyl monomer and exhibiting >=0.1l/g reduced viscosity (hereinafter abbreviated viscosity) in 0.1g/100ml chloroform at 25 deg.C with (B) a rubber-containing polymer synthesized by polymerizing 50 to 100wt.% methacrylate and 0 to 50wt.% vinyl monomer in an amount of 10 to 1000 pts.wt. in total in the presence of 100 pts.wt. elastic copolymer obtained by polymerization of 50 to 99.9wt.% alkyl acrylate, 0 to 40wt.% vinyl monomer and 0.1 to 10wt.% cross-linking monomer, (C) a thermoplastic polymer composed of 50 to 99wt.% 1 to 4C methacrylate, 1 to 50wt.% acrylate and 0 to 50wt.% vinyl monomer and exhibiting <=0.1l/g viscosity and (E) a delustering agent and exhibiting <=35000 poise melt viscosity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic matte film for laminating, which is laminated and used as a protective film for applications where matte is preferred.

[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. Applications where matte is preferred include wallpaper, furniture, vehicles. Conventionally, as the matte film for laminate, a matte film in which an organic or inorganic matte agent is mixed with a usual acrylic resin is used. Although various reports have been made on the matting agent to be blended, no report has been made so far regarding an acrylic resin which is a base material and is most suitable for lamination.

[0003]

The matte film in which an organic or inorganic matting agent is blended with the above-mentioned ordinary acrylic resin gives gloss during laminating and has a good matte state after lamination. It had the problem of not becoming.

[0004]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that the acrylic resin for a film, which is a base material, has a problem, and arrived at the present invention.

That is, according to the present invention, the thermoplastic polymer (I) shown below is 0.1 to 20 parts by weight, the rubber-containing polymer (II) is 5 to 99.9 parts by weight, and the thermoplastic polymer (III) is 0.
˜94.9 parts by weight, organic or inorganic matting agent 1 to 20 parts by weight, the total of (I) (II) (III) is 100 parts by weight, 180 ° C., shear rate 6.1 sec ⁻¹ A resin mixture having a melt viscosity of 35,000 poises or less at
It is a matte film for lamination obtained by forming a film.

(I) Thermoplastic polymer: 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of at least one other copolymerizable vinyl monomer. Dissolve 0.1 g of the combined product in 100 ml of chloroform and measure at 25 ° C.) to give 0.1 l
/ G thermoplastic resin (II) rubber-containing polymer 50 to 99.9% by weight of alkyl acrylate, 0 to 40% by weight of other copolymerizable vinyl monomer, and copolymerizable crosslinkable monomer 50% to 100% by weight of a methacrylic acid ester in the presence of 100 parts by weight of an elastic copolymer obtained by polymerizing a monomer mixture of 0.1 to 10% by weight of a monomer, and another vinyl monomer which can be copolymerized. Polymer containing rubber obtained by polymerizing 10 to 1000 parts by weight of monomer consisting of 0 to 50% by weight of monomer or mixture thereof (III) Thermoplastic polymer Methacrylic acid having alkyl group of 1 to 4 carbon atoms 50 to 99% by weight of ester, 1 to 50% by weight of acrylic acid ester, and at least one of other copolymerizable vinyl monomers.
0 to 50% by weight of seeds, reduced viscosity of polymer (polymer 0.1g is dissolved in chloroform 100ml, 25 ℃
Thermoplastic polymer having a melt viscosity of 0.1 l / g or less) is used in the present invention. By using a film obtained from a resin mixture having a limited melt viscosity, the matte state after lamination is improved. Is amazing.

The thermoplastic polymer (I) in the present invention is
Consists of 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of at least one other copolymerizable vinyl monomer, and the reduced viscosity of the polymer (0.1 g of the polymer is dissolved in 100 ml of chloroform, Measured at 25 ° C) is 0.1 l /
It is a thermoplastic polymer exceeding g and is a component that plays an important role in film moldability. Thermoplastic polymer (I)
The reduced viscosity is important, and if the reduced viscosity is 0.1 l / g or less, a film with good thickness accuracy cannot be obtained. The reduced viscosity is usually more than 0.1 l / g and not more than 2 l / g, preferably 0.2 to 1.2 l / g.

Thermoplastic polymer (I) used in the present invention
In the above, as the vinyl monomer copolymerizable with methyl methacrylate, an acrylic acid alkyl ester, a methacrylic acid alkyl ester, an aromatic vinyl compound, a vinyl cyan compound or the like can be used.

The thermoplastic polymer (I) 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 rubber-containing polymer (II) in the present invention is
It is a graft copolymer having a multilayer structure containing an acrylic acid alkyl ester as a main component of rubber, which has an effect of imparting excellent impact resistance and elongation to a resin composition.

The rubber-containing polymer (II) in the present invention is
Monomer mixture consisting of 50 to 99.9% by weight of alkyl acrylate, 0 to 40% by weight of other copolymerizable vinyl monomer, and 0.1 to 10% by weight of copolymerizable crosslinkable monomer. Monomer or mixture of 0 to 50% by weight of another vinyl monomer copolymerizable with 50 to 100% by weight of a methacrylic acid ester in the presence of 100 parts by weight of an elastic copolymer obtained by polymerizing ~ 1000 parts by weight at least 1
It is obtained by polymerizing in more than one stage.

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, in the present invention, a copolymerizable crosslinkable monomer is used. The crosslinkable monomer used is not particularly limited, but preferably ethylene glycol dimethacrylate, butanediol dimethacrylate,
Allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate, trimethylol triacrylate, allyl cinnamate, etc., can be used alone or in combination. You can

As the monomer to be grafted to the elastic copolymer, 50% by weight or more of a methacrylic acid ester is used, and specifically, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, Examples thereof include cyclohexyl methacrylate.
Further, 50% by weight or less of a copolymerizable vinyl-based monomer is used. Specific examples thereof include, but are not limited to, methyl acrylate, butyl acrylate, alkyl acrylates such as cyclohexyl acrylate, styrene and acrylonitrile. Can be mentioned. The monomer mixture to be grafted is 10 to 1000 with respect to 100 parts by weight of the elastic copolymer.
Parts by weight, preferably 20 to 200 parts by weight, are used and the polymerization can be carried out in at least one stage.

The rubber-containing polymer (II) in the present invention can be obtained by ordinary emulsion polymerization. A chain transfer agent must be used in order to set the melt viscosity within the range of the present invention. Known chain transfer agents can be used, but mercaptans are preferable. The amount of the chain transfer agent needs to be appropriately determined depending on the kind and composition of the monomer.

The thermoplastic polymer used in the present invention (II
I) is a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms of 50 to 99% by weight, an acrylic acid ester of 1 to
50% by weight and 0 to 50% by weight of at least one other vinyl monomer copolymerizable with them, and the reduced viscosity of the polymer (0.1 g of the polymer is dissolved in 100 ml of chloroform and (Measured) is 0.1 l / g or less.

As the methacrylic acid ester used in the thermoplastic polymer (III), 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 1 to 50% by weight, preferably 5
-40% by weight. By using the acrylic ester, the melt viscosity is lowered, and it becomes easy to set the melt viscosity within the range of the present invention. Known monomers can be used as the other copolymerizable vinyl monomer.

The method for producing the thermoplastic polymer (III) is not particularly limited, but it can be polymerized by a usual suspension polymerization method, emulsion polymerization method, bulk polymerization method or the like. A chain transfer agent must be used in order to set the melt viscosity within the range of the present invention. Known chain transfer agents can be used, but mercaptans are preferable. The amount of chain transfer agent is monomer type,
It needs to be appropriately determined depending on the composition.

The present invention provides a thermoplastic polymer (I), a rubber-containing polymer (II), and a thermoplastic polymer (II) thus obtained.
A matte film for laminating obtained by forming a film from a resin mixture comprising I) and an organic or inorganic matting agent. The thermoplastic polymer (I), the rubber-containing polymer (II), and the thermoplastic polymer (III) are used in a total amount of 100 parts by weight, and the mixing ratio is 0.1 to 20 parts by weight of the thermoplastic polymer (I). Parts, the rubber-containing polymer (II) is 5 to 99.9 parts by weight, and the thermoplastic polymer (III) is 0 to 94.9 parts by weight. In the present invention, it is essential to use 1 to 20 parts by weight of an organic or inorganic matting agent. The type of matting agent is not particularly limited, and known ones can be used. Preferably, as the organic matting agent, resin fine particles having a crosslinked structure having a particle size of 1 to 20 μm, and 50 to 90% by weight of a vinyl aromatic monomer.
And 10 to 50% by weight of acrylic acid ester or methacrylic acid ester having an alkyl group having 1 to 13 carbon atoms
And at least one kind of other vinyl monomer copolymerizable therewith 0 to 40% by weight, and an allyl compound having two or more copolymerizable double bonds in the molecule 0.5 to 5% by weight When,
Resin fine particles having an average particle size of 35 to 500 μm obtained by suspension polymerization of a monomer mixture consisting of 0 to 5% by weight of a crosslinkable monomer copolymerizable with these, and mica fine particles as an inorganic matting agent. , Or talc particles.

The resin fine particles having a crosslinked structure and having a particle diameter of 1 to 20 μm are preferably acrylic resin fine particles and are fine particles which are crosslinked by a crosslinking agent and do not melt. Acrylic resin-based fine particles will improve the transparency of the film, and if meltable fine particles are used, a good matting effect cannot be expected.

Examples of the vinyl aromatic monomer used in the resin fine particles having an average particle diameter of 35 to 200 μ include styrene, vinyltoluene, α-methylstyrene, halogenated styrene and the like. Examples of the acrylic acid ester or methacrylic acid ester having an alkyl group having 1 to 13 carbon atoms include ethyl acrylate, butyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. Known monomers can be used as the copolymerizable vinyl monomer. Examples of the allyl compound having two or more copolymerizable double bonds in the molecule include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Examples of other crosslinkable monomers include ethylene glycol dimethacrylate
, Propylene glycol diallyl ether, divinylbenzene and the like.

These matting agents are used in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight. If it is less than 1 part by weight, good matting properties cannot be expected, and if it exceeds 20 parts by weight, the appearance of the molded product may be impaired.

The melt viscosity of the resin composition of the present invention is 1
35,000 at 80 ℃, share rate 6.1sec ^-1
Poise or less, preferably 30,000 poise or less,
It is more preferably 25,000 poise or less. If the melt viscosity exceeds 35,000 poise, good matteness cannot be exhibited after laminating.

The resin composition of the present invention may contain, if necessary, general compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact resistance aids, foaming agents, fillers, colorants, and ultraviolet absorbers. Can be included.

The resin composition of the present invention is formed into a film. Prior to molding, it is preferable that predetermined amounts of each are sufficiently uniformly mixed using a Henschel mixer or the like, melt-kneaded at 160 to 280 ° C. using a screw extruder or the like, and molded into pellets. After that, a good matte film can be obtained by a T-die method, an inflation method, a calendar method, or the like. The film obtained in the present invention can be laminated on various base resins, films and the like by a usual laminating method, but it is preferable to perform thermal lamination at 50 to 180 ° C.

[0027]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In the examples, all parts are based on weight.

Examples 1 to 9 a) Production of thermoplastic polymer (I) A reactor was charged with 200 parts of nitrogen-exchanged deionized water, 1 part of an emulsifier potassium oleate and 0.3 part of potassium persulfate. . Subsequently, 40 parts of methyl methacrylate, 10 parts of n-butyl acrylate, and 0.0 of n-octyl mercaptan.
05 parts were charged and the polymerization was completed by stirring at 65 ° C. for 3 hours under a nitrogen atmosphere. Subsequent methyl methacrylate 48
Part, and a monomer mixture consisting of 2 parts of n-butyl acrylate were added dropwise over 2 hours and maintained for 2 hours after completion of the addition 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. The reduced viscosity ηsp / c of the obtained copolymer was 0.38 l / g.

B) Manufacture of rubber-containing polymer (II) The following proportions of raw materials were charged into 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 (BA) 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 0.5 part Sodium hydrogen phosphate dihydrate 0.3 part 100 parts by weight of this elastic latex (as solid content) was placed in a reaction vessel, and nitrogen substitution was carried out while stirring.
After raising the temperature to 0 ° C. and adding an aqueous solution consisting of 0.125 parts of sodium formaldehyde sulfoxylate and 2 parts of deionized water, while maintaining the temperature at 80 ° C., 60 parts of methyl methacrylate, 0.05 parts 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 added to a 3% saline solution, and after salting out, dehydration, washing with water and washing were carried out to obtain a rubber-containing polymer (II) -1 in powder form.

C) Manufacture of Molded Articles The thermoplastic polymer (I), the rubber-containing polymer (II) and the thermoplastic polymer (III) obtained as described above are methyl methacrylate / methyl acrylate copolymers. Polymer (methyl methacrylate / methyl acrylate = 75/25, ηsp / c =
0.02 l / g) and various matting agents were mixed in various ratios shown in Table 1 in a Henschel mixer. The average particle size is 35
As the resin fine particles of 500 μ, METABLEN F-410
(Styrene, butyl acrylate, methyl methacrylate, allyl methacrylate copolymer (a matting agent for vinyl chloride manufactured by Mitsubishi Rayon Co., Ltd.) was used. Then, using a 40 mmφ screw type extruder (L / D = 26), the cylinder temperature was 2
The mixture was melt-kneaded and pelletized at a temperature of 00 to 260 ° C and a die temperature of 250 ° C. Table 1 shows the melt viscosity of the obtained pellets at a 180 ° C. share rate of 6.1 sec ⁻¹ .

The obtained pellets are dried with a dehumidifying drier 50
The film was dried at ℃ for 1 day and then formed into a film by using a T-die. Table 1 shows the moldability and glossiness of the obtained film.
The glossiness was measured at 60 ° using a gloss meter (GM-26D type manufactured by Murakami Color Research Laboratory).

D) Lamination A film obtained by the above method was laminated with a soft vinyl chloride film having a thickness of 100 μ using a laminating roll with embossing.
Thermal lamination was performed under the conditions of 50 ° C. and 30 kg / cm ² . The gloss of the obtained film after lamination is shown in Table 1.
Shown in.

Examples 10 to 14 a) Production of Rubber-Containing Polymer (II) In the same manner as in Example 1-b, elastic latexes containing acrylate as a main component were obtained. To 100 parts by weight of this elastic latex (as solid content), methyl methacrylate 6 was added.
Grafting was carried out in the same manner as in Example 1-b except that 0 parts and 0.05 parts of n-octyl mercaptan were used instead of 60 parts of methyl methacrylate, 20 parts of methyl acrylate and 0.8 parts of n-octyl mercaptan. Polymerization was performed to obtain a rubber-containing polymer (II) -2.

B) Production of Molded Articles The thermoplastic polymer (I) obtained in Example 1-a, the rubber-containing polymer (II) -1 and the rubber-containing polymer (II) -obtained by the above method. 2, various thermoplastic polymers shown in Table 2 (II
I) and various matting agents were used to obtain a film in the same manner as in Example 1, and a soft vinyl chloride film was laminated in the same manner as in Example 1. Table 2 shows the evaluation results of the pellet, the film, and the film after lamination.

Comparative Example 1 A film was formed in the same manner as in Example 1 without using the thermoplastic polymer (I). The results are shown in Table 1. From this comparative example, it is understood that a good film cannot be obtained unless the thermoplastic polymer (I) is used.

Comparative Examples 2 to 3 Films were obtained in the same manner as in Example 1 except that the type and amount of the matting agent were changed as shown in Table 1, and the film was laminated on a soft vinyl chloride film. The results are shown in Table 1. Table 1
It can be seen that when the amount of the matting agent is less than 1 part by weight, good matting properties cannot be obtained, and when the amount of the matting agent exceeds 20 parts by weight, the film appearance is impaired.

Comparative Examples 4 to 5 Films were obtained in the same manner as in Example 1 except that the thermoplastic polymer (III) shown in Table 2 was used, and the film was laminated on a soft vinyl chloride film. The results are shown in Table 2.
From Table 2, 180 ° C share rate of pellets 6.1sec
^It can be seen that when the melt viscosity at ^-1 exceeds 35,000 poise, the glossiness after lamination is high and the matting property becomes poor.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

The matte film obtained by forming a film from the resin mixture of the present invention has a good matteness after laminating, and is suitable as a protective film for wallpaper, furniture, vehicles and the like where matte is preferred. Can be used for

Claims (4)

[Claims] 1. A thermoplastic polymer (I) shown below.
1 to 20 parts by weight, rubber-containing polymer (II) 5 to 99.9 parts by weight, thermoplastic polymer (III) 0 to 94.9 parts by weight, organic or inorganic matting agent 1 to 20 parts by weight , (I)
The total of (II) and (III) is 100 parts by weight, and 180
Melt viscosity at ℃, shear rate 6.1sec ^-1 is 3500
A matte film for laminating obtained by forming a film of a resin mixture having a poise of 0 or less. (I) Thermoplastic polymer 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of at least one other copolymerizable vinyl monomer, and the reduced viscosity of the polymer (polymer 0. 1 g was dissolved in 100 ml of chloroform and measured at 25 ° C) was 0.1 l
/ G thermoplastic resin (II) rubber-containing polymer 50 to 99.9% by weight of alkyl acrylate, 0 to 40% by weight of other copolymerizable vinyl monomer, and copolymerizable crosslinkable monomer 50% to 100% by weight of a methacrylic acid ester in the presence of 100 parts by weight of an elastic copolymer obtained by polymerizing a monomer mixture of 0.1 to 10% by weight of a monomer, and another vinyl monomer which can be copolymerized. Polymer containing rubber obtained by polymerizing 10 to 1000 parts by weight of monomer consisting of 0 to 50% by weight of monomer or mixture thereof (III) Thermoplastic polymer Methacrylic acid having alkyl group of 1 to 4 carbon atoms 50 to 99% by weight of ester, 1 to 50% by weight of acrylic acid ester, and at least one of other copolymerizable vinyl monomers.
0 to 50% by weight of seeds, reduced viscosity of polymer (polymer 0.1g is dissolved in chloroform 100ml, 25 ℃
Thermoplastic polymer having a value of 0.1 l / g or less) 2. The matte film for laminate according to claim 1, wherein the matting agent is resin fine particles, mica fine particles, or talc fine particles having a particle size of 1 to 20 μm and having a crosslinked structure. 3. The matte film for laminating according to claim 1, wherein the matting agent is one shown below. 50 to 90% by weight of a vinyl aromatic monomer, 10 to 50% by weight of an acrylate or methacrylic acid ester having an alkyl group having 1 to 13 carbon atoms, and at least one other copolymerizable vinyl monomer 0 to 40% by weight, an allyl compound having two or more copolymerizable double bonds in the molecule.
5 to 5% by Weight and Crosslinkable Monomer Copolymerizable with These
Resin fine particles having an average particle size of 35 to 500μ obtained by suspension polymerization of a monomer mixture consisting of 4. The matte film for laminating according to claim 1, which is a film laminated on a vinyl chloride film or sheet.