JPH09100385A - Acrylic resin composition for calendering - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a resin compsn. for calendering which can offer a molding having excellent weather resistance and impact resistance by incorporating a predetermined amt. of a lubricant into an acrylic resin selected from a particular acrylic rubber elastomer and an acrylic polymer. SOLUTION: This acrylic rubber elastomer comprises 30 to 80wt.% rubber layer prepd. from 60 to 99.5wt.% alkyl acrylate having a 1-8C alkyl group, 0 to 39.5wt.% polymerizable monofunctional vinyl monomer, and 0.5 to 5wt.% polyfunctional monomer having a plurality of vinyl groups or vinylidene groups; and 70 to 20wt.% hard resin prepd. from 40 to 100wt.% methyl methacrylate, 0 to 60wt.% alkyl acrylate, and 0 to 20wt.% polymerizable vinyl or vinylidene monomer, the elastomer further comprising an outermost layer of a hard resin. Into 100 pts.wt. acrylic resin selected from acrylic polymers prepared from this elastomer and 50 to 100wt.% methyl methacrylate is incorporated 0.1 to 4 pts.wt. lubricant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an acrylic resin composition for calender molding, which can be molded into a sheet or film by calender molding, and the obtained sheet or film has weather resistance and transparency. It can be applied to wallpaper and outdoor signboards with excellent properties.

[0002]

BACKGROUND OF THE INVENTION It is known that calendering is superior in productivity to other extrusion molding and injection molding and can easily produce a wide sheet or film. .

As a resin molded by calendering, a polyvinyl chloride (PVC) resin ranging from hard to soft is generally used, and it is used for packaging materials, wallpaper and the like.

In particular, flexible PVC is used for agricultural house members (agricultural plastics), outdoor signboards, road displays, marking films for vehicles, and the like.

However, in the case of PVC resin, the weather resistance is poor and the change in color is large, and a large amount of hydrogen chloride gas is generated when the polymer is incinerated.

On the other hand, acrylic resins have been used for injection molding, extrusion molding, etc., but they are inferior in impact resistance and in metal releasability.
It was never formed into a film.

As a result of intensive studies to solve the above problems, the present inventors have found that calender molding can be performed by adding a lubricant to an acrylic resin, and have arrived at the present invention. The calendar-molded acrylic resin sheet / film obtained by the present invention has excellent weather resistance and transparency. Further, since the acrylic resin is used, there is no need to worry about the generation of hydrogen chloride gas when the polymer is incinerated, unlike the case of PVC resin.

[0008]

The gist of the present invention is that the alkyl group has 60 to 99.5% by weight of an alkyl acrylate having 1 to 8 carbon atoms and one vinyl group copolymerizable therewith. Rubber layer 3 obtained from 0 to 39.5% by weight of a monofunctional monomer having 0.5 to 5% by weight of a polyfunctional monomer having at least two vinyl groups or vinylidene groups.
0 to 80% by weight, methyl methacrylate 40 to 100% by weight, alkyl acrylate having an alkyl group having 1 to 8 carbon atoms 0 to 60% by weight, and vinyl or vinylidene monomer 0 to 20% by weight copolymerizable therewith. An acrylic rubber-like elastic body (A-) in which at least the outermost layer is a hard resin, which is composed of 20 to 70 wt% of a hard resin obtained from
1) and 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of another vinyl monomer copolymerizable therewith, at least one acrylic resin (A-2) selected from acrylic polymers (A-2). ) 0.1 to 4 parts by weight of the lubricant (B) is mixed with 100 parts by weight of the acrylic resin composition for calendar molding.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylic resin used in the present invention is an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms in an amount of 60 to 99.5% by weight, and one vinyl group copolymerizable therewith. 30 to 80% by weight of a rubber layer obtained from 0 to 39.5% by weight of a monofunctional monomer having 0.5 to 5% by weight of a polyfunctional monomer having at least two vinyl groups or vinylidene groups, and methyl methacrylate. 40-1
00% by weight, 0-60% by weight of an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, and 20-70% by weight of a hard resin obtained from 0-20% by weight of a vinyl or vinylidene monomer copolymerizable therewith. Obtained from acrylic rubber-like elastic body (A-1) in which at least the outermost layer is a hard resin, 50 to 100% by weight of methyl methacrylate, and 0 to 50% by weight of other vinyl monomer copolymerizable therewith. Is at least one selected from the acrylic polymers (A-2).

The acrylic rubber-like elastic body (A-1) includes a rubber layer which is a main constituent unit obtained from an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms in its resin composition, and Is a graft copolymer in which a hard resin layer whose main component is a unit derived from methyl methacrylate. The rubber layer has a glass transition point (hereinafter referred to as T
(abbreviated as g) is an elastic body having a temperature of 25 ° C. or less, in which a resin layer containing a unit derived from a hard methyl methacrylate having the same or different composition as the outermost layer as a main component is present. May be

The particle size of the acrylic rubber-like elastic material (A-1) is usually in the range of 0.1 to 0.4 μm.

The hard resin layer is a hard resin having a Tg of 25 ° C. or higher, preferably 40 to 100 methyl methacrylate.
% And 0 to 60% by weight of alkyl acrylates having 1 to 8 carbon atoms and 0 to 20% by weight of monofunctional or polyfunctional vinyl or vinylidene monomers copolymerizable with these monomers.

The alkyl acrylate having 1 to 8 carbon atoms in the alkyl group is not particularly limited, but preferably,
Examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate.

The vinyl or vinylidene monomer copolymerizable with the above-mentioned alkyl acrylate is not particularly limited, but monofunctional monomers are preferably aromatic vinyl such as styrene, vinyl cyanide such as acrylonitrile, cyclohexylmaleimide and the like. Is a maleic acid derivative of.

The polyfunctional monomers include difunctional monomers such as ethylene dimethacrylate, allyl methacrylate, allyl cinnamate, allyl sorbate and diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate and trimethylol. Trifunctional monomers such as propanetriacrylate, triallyl fumarate and triallyl maleate, and tetrafunctional monomers such as pentaerythritol tetraacrylate and pyromellitic acid tetraacrylate can be used alone or in combination.

In obtaining the hard resin layer, if necessary, a thiol compound such as octyl mercaptan may be added as a polymerization chain transfer agent to control the molecular weight.

The acrylic rubber layer comprises 60 to 99.5% by weight of alkyl acrylate having 1 to 8 carbon atoms in the alkyl group,
It is obtained from 39.5 to 0% by weight of another vinyl monomer copolymerizable therewith and 0.5 to 5% by weight of a multifunctional vinyl or vinylidene monomer.

The alkyl acrylate having an alkyl group having 1 to 8 carbon atoms is not particularly limited, but is preferably ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or the like. The copolymerizable vinyl monomer is not particularly limited, and the same type as that used for the hard resin layer can be used.

Further, the copolymerizable polyfunctional vinyl or vinylidene monomer is not particularly limited, and the same type as that used for the hard resin layer can be used.

The acrylic copolymer (A-
2) is obtained from 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of another vinyl monomer copolymerizable therewith.

The other vinyl monomer copolymerizable with methyl methacrylate is not particularly limited, and the same type as that used for the hard resin layer can be used.

The method for producing each resin component is not particularly limited, but emulsion polymerization is preferred. The polymerization temperature is 50 to 160 ° C. although there are some differences depending on the polymerization method.

As the lubricant (B) used in the present invention,
Typical examples are fatty acid metal salts of stearic acid such as calcium, magnesium, zinc and barium, polyethylene wax, polymeric lubricants such as acrylic lubricants (metabrene L-1000) provided by Mitsubishi Rayon Co., Ltd., and montanic acid esters. Examples of the ester-based lubricants include

The amount of the lubricant (B) blended is 0.1 to 4 parts by weight per 100 parts by weight of the acrylic resin (A). When the amount is less than 0.1 part by weight, the metal peeling property, which is important in calendar molding, is not sufficient, and when it exceeds 4 parts by weight, transparency and weather resistance tend to be impaired, which is not preferable.

Further, when softening the acrylic resin (A), in addition to the lubricant (B), a plasticizer (C) such as a phthalate ester, a polyester plasticizer, an epoxy plasticizer or the like is further added. For 100 parts by weight of acrylic resin,
10 to 100 parts by weight can be blended.

Specific examples of the plasticizer (C) include di-n-octyl phthalate, dibutyl phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, dilauryl isophthalate, dibutyl lauryl terephthalate, Phthalates such as butylbenzyl phthalate, aliphatic dibasic acid esters such as di (2-ethylhexyl) adipate, di (2-ethylhexyl) sebacate, di (2-ethylhexyl) azelate, tributyl citrate , Acetyl tri (2-ethylhexyl) citrate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, trioctyl trimellitate, tetraoctyl pyromellitic acid, tri (2-ethylhexyl) phosphate, trioctyl phosphate, phosphorus Acid diphenyloctyl etc. Also, these and other secondary plasticizers,
For example, polypropylene glycol adipate, polypropylene glycol sebacate, epoxidized soybean oil and rapeseed oil, epoxy compounds containing compounds such as isobutyl ester and octyl ester of these epoxidized fatty acids, chlorinated paraffin, etc. It can be used together from the viewpoint.

Further, it is preferable to add a vinyl chloride resin in order to further enhance the releasability of the sheet and roll obtained during calendering. The vinyl chloride resin (D) can be added in an amount of 10 to 50 parts by weight based on 100 parts by weight of the acrylic resin. From the viewpoint of weather resistance, the blending amount is preferably 50 parts by weight or less.

In order to further improve the calender moldability, an acrylic processing aid added to a vinyl chloride resin (for example, Metabrene P-530 manufactured by Mitsubishi Rayon Co., Ltd.).
A) may be added in an amount of 5 parts by weight or less based on 100 parts by weight of the acrylic resin. In the present invention, substances other than the above can be added and mixed as necessary.

Examples of these include antistatic agents, antioxidants, ultraviolet absorbers, color pigments, dyes, anti-condensation agents and the like.

Examples of antistatic agents include nonionic activators such as glycerin monostearate and behenyl alcohol, anionic activators such as sodium alkylbenzene sulfonate, and cationic activators containing quaternary ammonium salts.

Examples of the antioxidants include P-containing substances such as trisnonylphenyl phosphite, S-containing compounds such as dilauryl thiodipropionate, and hindered phenol compounds.

Examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, salicylate compounds, and hindered amine compounds as light stabilizers.

As the coloring pigments, dyes, anti-condensation agents and the like, known ones which are usually used are used.

When a sheet or film is produced by calender molding using the resin composition of the present invention, the method is not particularly limited, but for example, it is fed to a calendering device after being mixed with a Henschel mixer or a tumbler type blender. .

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments.

"Parts" or "%" in the description means parts by weight or% by weight. The test items for evaluating the obtained film, the contents thereof, and the measuring method are as follows.

(Weather resistance) Accelerated exposure tester (Sunshine Carbon Arc tester manufactured by Suga Tester Co., Ltd.) was used for 1100 hours at a back panel temperature of 63 ° C. for 12 hours per hour.
It was carried out under a rainfall condition of a minute. The dye (ΔE) of this sample before and after the test was measured according to JIS K-7105.

(Tensile Elongation) The tensile elongation was measured before and after the accelerated exposure test according to JIS C-2318.

(Transparency) 5 cm from each film obtained
It was cut into a size of 5 cm, and the total light transmittance and the haze value were measured according to (JIS K7105 · A method).

(Impact of falling weight) Using the obtained film,
The 50% fracture height (H50) and the fracture energy (E50) were measured by the method according to JIS K-7211. The weight of the falling weight was 500 g.

(Examples 1 to 9 and Comparative Examples 1 to 3) I) Manufacture of acrylic rubber-like elastic body (A-1 (1)) (1) Manufacture of innermost layer 100 liters of internal volume equipped with a stirrer 25 kg of deionized water, 100 g of boric acid, 10 g of sodium carbonate, 0.01 g of ferrous sulfate, 0.04 g of ethylenediaminetetraacetic acid disodium and 8 g of an emulsifier (sodium N-lauroylsarcosine), methyl methacrylate (hereinafter referred to as MMA). ) 730 g, methyl acrylate (hereinafter MA) 40 g, 1,3-butylene glycol dimethacrylate 32 g (hereinafter BDMA) and tert-butyl hydroperoxide (hereinafter tBH) 2.4 g are put all at once, and nitrogen gas is blown into the substance. After making the state in which there is no effect of oxygen, raise the temperature to 80 ° C and add sodium formaldehyde. A 10% aqueous solution of de sulfoxylate (hereinafter SFS) was added, polymerization was carried out for 60 minutes. Then MMA11
00g, MA 60g, BDMA 48g and tBH3.
6 g was continuously added and polymerized for 30 minutes, and the polymerization was continued for another 90 minutes after the addition was completed.

(2) Production of rubber layer In an autoclave containing 2 kg of the first stage product obtained in the above (1), 20 g of SFS and 50 g of emulsifier (sodium N-lauroylsarcosine) in 500 g of deionized water.
Butyl acrylate (hereinafter BA) 81%, styrene (hereinafter St) 17.5%, triallyl isocyanate 1.1%, 1,4 butanediol-diacrylate 0.3% are added. Monomer mixture 8 consisting of
Polymerization was carried out by continuously adding 32 g of tBH to 150 kg over 150 minutes, and further adding 1 after completion of the addition.
Polymerization was continued for 80 minutes.

(3) Production of Hard Resin Layer Next, 500 g of 10% emulsifier aqueous solution was added to the same container containing the polymer latex containing 10 kg of the rubber layer obtained in the above (2), and the internal temperature was adjusted to 80 ° C. Hold, MMA95
%, MA 5%, n-octyl mercaptan 0.4%, t
A monomer mixture containing 0.2% of BH was continuously added for 90 minutes for polymerization for 90 minutes, and after the addition was completed, the polymerization was further continued for 60 minutes.

A polymer latex containing an acrylic rubber-like elastic material (A-1 (1)) was obtained by the above series of polymerization methods. The particle size of this polymer latex measured by an absorbance method was 0.3 μm. This polymer latex was coagulated in 1% sulfuric acid water at 70 ° C., washed with deionized water, dehydrated, and air-dried at 80 ° C. to obtain an acrylic rubber-like elastic body (A-1 (1)) in powder form. Got with.

II) Acrylic rubber-like elastic material (A-1
Production of (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.

BA 77 parts St 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 Hydrogen phosphate Sodium dihydrate 0.3 part 100 parts by weight of this elastic latex (as a solid content) was placed in a reaction vessel, and the atmosphere was sufficiently replaced with nitrogen while stirring.
After raising the temperature to 0 ° C. and adding an aqueous solution of 0.125 parts of sodium formaldehyde sulfoxylate and 2 parts of deionized water, 57 parts of MMA and MA while maintaining the temperature at 80 ° C.
3 g, n-octyl mercaptan 0.05 part, tBH
After dropping a mixture of 0.125 parts over 2 hours, 2
Hold for time to complete the polymerization. The obtained copolymer latex was salted out, dehydrated, washed with water and washed to obtain a powdery acrylic rubber-like elastic material (A-1 (2)).

Acrypet MF (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) was used as the acrylic polymer (A-2).

Next, the acrylic rubber-like elastic material (A
-1 (1), A-1 (2)), acrylic polymer (A-
2), lubricant (B), various auxiliaries shown in Table 1, Tinuvin P
(UV absorbers manufactured by Ciba Geigy Co., Ltd.) ((A) +
(B) + (C) = 0.03 parts by weight with respect to 100 parts by weight), ADEKA STABMARK 329 (Adeka Argus Co., Ltd., antioxidant part) ((A) + (B) + (C) = 1
0.2 parts by weight with respect to 00 parts by weight) were mixed for 5 minutes in a Henschel mixer at a ratio shown in Table 1.

500 g of this resin composition was kneaded with an 8-inch roll under the following conditions: rotation speed: 14 to 17 rpm, 160 ° C., 5 minutes. This is pressed at 180 ° C. and 0.5
A mm compression sheet was created.

With respect to this sheet, the items of the previous term were evaluated and the results shown in Table 1 were obtained.

[0051]

[Table 1]

[0052]

INDUSTRIAL APPLICABILITY The resin composition of the present invention can provide a sheet / film excellent in weather resistance and impact resistance by calender molding with less problems during incineration.

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Claims (3)

[Claims] 1. An alkyl acrylate having an alkyl group having 1 to 8 carbon atoms in an amount of 60 to 99.5% by weight, a monofunctional monomer having one vinyl group copolymerizable with the alkyl group in an amount of 0 to 39.5% by weight, and 30 to 80% by weight of a rubber layer obtained from 0.5 to 5% by weight of a polyfunctional monomer having at least two vinyl groups or vinylidene groups, and 40 to 40% of methyl methacrylate.
From 100% by weight, 0 to 60% by weight of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, and 20 to 70% by weight of a hard resin obtained from 0 to 20% by weight of a vinyl or vinylidene monomer copolymerizable therewith. 50% to 100% by weight of acrylic rubber-like elastic body (A-1) composed of at least the outermost layer made of a hard resin and methyl methacrylate
And other vinyl monomers copolymerizable therewith 0-50
Calender prepared by blending 0.1 to 4 parts by weight of the lubricant (B) with 100 parts by weight of at least one acrylic resin (A) selected from the acrylic polymer (A-2) obtained by weight%. Acrylic resin composition for molding. 2. The plasticizer (C) according to claim 1, further comprising: 10 parts by weight of plasticizer (C) with respect to 100 parts by weight of acrylic resin (A).
An acrylic resin composition for calendar molding, which comprises 100 parts by weight. 3. The acrylic resin composition for calendar molding according to claim 1, further comprising 10 to 50 parts by weight of a vinyl chloride resin (D) with respect to 100 parts by weight of the acrylic resin (A).