JP2002128978A - Vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin composition which exerts an extremely small change in its hardness caused by the change of temperature associated with the change of seasons, etc. SOLUTION: The vinyl chloride resin composition is prepared by compounding 100 pts.wt. vinyl chloride resin with from 15 to 100 pts.wt. plasticizer and from 10 to 200 pts.wt. copolymer containing from 20 to 60 wt.% methyl methacrylate monomer unit, from 10 to 60 wt.% acrylic ester monomer unit and from 1 to 20 wt.% styrene monomer unit as constituents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition and a film or sheet obtained by molding the composition. More specifically, the present invention relates to a vinyl chloride resin composition used for decorative films, stickers, surface protection films such as marking films and steel plates, partitions, stationery, toys, and the like, and a film or sheet formed by molding the composition. is there.

[0002]

2. Description of the Related Art A plasticizer is usually added to a soft vinyl chloride resin film and a semi-rigid vinyl chloride resin film as a resin softener, but these vinyl chloride resin films are sensitive to the influence of the plasticizer. The temperature increases,
The film hardness is soft at summer temperatures and hard at winter temperatures. Therefore, when processing these films, there are drawbacks such as the need to significantly change the processing conditions of the film depending on the season, and in order to solve the drawback, the film processed in winter is processed more than the film processed in summer. The hardness may be adjusted by changing the amount of plasticizer depending on the season to be processed, such as increasing the amount of plasticizer added to the film. However, when the blending amount of the plasticizer is increased for processing in winter, it is known that when a product using this film is subjected to high temperatures in summer or the like, the film becomes sticky or causes a defect such as sagging. . In addition, if this film is stored over a film with a small amount of plasticizer for processing in the summer, wrinkles due to migration of the plasticizer may occur, and the film may not be handled as the same product. is there. Therefore, the actual amount of the plasticizer in the film is limited to about 3 to 5 parts by weight for processing in the winter, but there is no sufficient effect, and the change in hardness under a temperature change due to seasonal differences is not achieved. Can not be completely suppressed, it was not possible to eliminate the condition adjustment at the time of processing.

Further, in order to improve the physical properties of the film at low temperatures without increasing the amount of the plasticizer, adipic acid having an average degree of branching of less than 0.5 and having an alkyl group having 6 to 10 carbon atoms is used. A method of blending an ester plasticizer has been proposed (JP-A-58-49742, etc.).
However, this method has a disadvantage that the compatibility between the plasticizer and the vinyl chloride resin is poor, and the plasticizer bleeds or is inferior in heat resistance. Further, there was almost no effect of reducing a difference in film hardness due to a change in temperature due to a seasonal change or the like.

[0004]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies with the aim of providing a molded article of a vinyl chloride resin in which the change in hardness due to temperature change such as seasonal change is extremely small. It has been found that the above objects can be achieved by blending a plasticizer and a specific copolymer into the present invention, and the present invention has been accomplished.

[0005]

The gist of the present invention is to provide a plasticizer of 15 to 100 parts by weight per 100 parts by weight of a vinyl chloride resin.
Parts by weight, 20 to 60% by weight of methyl methacrylate, 10 to 60% by weight of acrylate ester, and styrene monomer 1
Copolymer containing 10 to 20% by weight as a component
A vinyl chloride resin composition containing 200 parts by weight and a film or sheet obtained by molding the composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 1. Vinyl Chloride Resin In the present invention, the vinyl chloride resin refers to a homopolymer of vinyl chloride, a polymer of vinyl chloride and a comonomer copolymerizable therewith, and a mixture of these polymers. The vinyl chloride resin may be produced by any of known production methods such as a suspension polymerization method, a bulk polymerization method, a fine suspension polymerization method, and an emulsion polymerization method. Examples of the comonomer include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylates such as methyl methacrylate and ethyl methacrylate; and dibutyl. Maleates such as maleate and diethyl maleate; fumaric esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; cyanides such as acrylonitrile and methacrylonitrile Vinyl chloride, ethylene, propylene,
Examples thereof include polyfunctional monomers such as α-olefins such as styrene, vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, and vinylidene halides, diallyl phthalate, and ethylene glycol dimethacrylate. Of course, the comonomer is not limited to those described above. The comonomer may be contained in an amount of 30% by weight or less, preferably 20% by weight or less in the constituent components of the vinyl chloride resin.

[0007] The category of the vinyl chloride resin also includes a chlorinated vinyl chloride resin obtained by post-chlorinating the vinyl chloride resin produced as described above. Furthermore, in the present invention, it is preferable to use, as the vinyl chloride resin, those having an average degree of polymerization of 700 or more, preferably 800 or more, and 2500 or less, preferably 1300 or less. You may mix and use 2 or more types. As a mixing method, 2
Generally, two or more types of resins are mixed, but by controlling the polymerization conditions during polymerization of the vinyl chloride resin, two or more types of vinyl chloride resins having apparently different average degrees of polymerization were mixed. May be used. 2. Acrylic copolymer In the present invention, a copolymer containing 20 to 60% by weight of methyl methacrylate, 10 to 60% by weight of an acrylate ester, and 1 to 20% by weight of a styrene-based monomer (hereinafter, referred to as "a"). (Acrylic copolymer) is added in an amount of 10 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin.

[0008] By using the acrylic copolymer having the above structure, it is possible to obtain a molded article made of a vinyl chloride resin, in which the change in hardness due to temperature change such as seasonal change is extremely small, that is, the temperature sensitivity is small. . Further, a molded article such as a film or a sheet can be formed without impairing the appearance. In particular, in the calender molding, since the rotation of the bank (the pool of resin between the rolls) does not become uneven and the peeling of the resin from the rolls does not deteriorate, molding of a film or sheet having a good appearance is performed. Goods can be obtained.

When the amount of the acrylic copolymer is small,
The effect of suppressing the change in hardness of the molded article due to the temperature change is not sufficient, and if the compounding amount is too large, the elongation of the molded article is inferior, and the film or sheet may be broken during processing such as printing of the film or sheet. . As the acrylate, alkyl acrylate is preferable, and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate and phenyl acrylate These may be used alone or in combination of two or more. Of these, butyl acrylate and methyl acrylate are preferred.

As the styrene monomer, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene,
Isobutyl styrene, tertiary butyl styrene, o
-Bromostyrene, m-bromostyrene, p-bromostyrene, o-chlorostyrene, m-chlorostyrene, p
-Chlorostyrene and the like, and may be used alone or in combination of two or more. Of these, styrene is preferred.

The acrylic copolymer may contain, in addition to the above-mentioned monomers, monomers copolymerizable therewith as copolymerizable components. Examples of the monomers include vinyl cyanine compounds, Examples include polymerizable unsaturated acids, maleimides, unsaturated carboxylic anhydrides, epoxy group-containing unsaturated compounds, amino group-containing unsaturated compounds, acrylamide compounds, monofunctional monomers, polyfunctional monomers, and the like. These are preferably blended so as to be 30% by weight or less based on the total amount of methyl methacrylate, acrylate and styrene monomer. Examples of the polymerizable unsaturated acid include itaconic acid, maleic acid, fumaric acid, crotonic acid, and cinnamic acid. Examples of the monofunctional monomer include acrylonitrile and vinyl acetate. Examples of the polyfunctional monomer include allyl methacrylate and triallyl cyanurate. 3. Plasticizer The plasticizer is used in an amount of 15 parts by weight per 100 parts by weight of the vinyl chloride resin.
An appropriate amount may be selected from this range as appropriate, depending on the application. The amount of plasticizer is 2
Particularly preferred is 0 to 40 parts by weight.

The plasticizer that can be used is not particularly limited as long as it is commonly used for vinyl chloride resins. For example, dibutyl phthalate (DBP), dihexyl phthalate, di-2-ethylhexyl phthalate (DOP) Phthalate plasticizers such as di-n-octyl phthalate and diisodecyl phthalate; aliphatic dibasic ester plasticizers such as dioctyl adipate, diisodecyl adipate and dioctyl sebacate; trioctyl trimellitate (TOTM); Trimellitic ester plasticizers such as decyl trimellitate; tricresyl phosphate (TCP), triphenyl phosphate, trixylyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate , Tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dichloro-propyl) phosphate plasticizers such as phosphates,
Examples include polyester-based polymer plasticizers, epoxidized soybean oil, epoxidized linseed oil, and epoxy-based plasticizers such as liquid epoxy resin. These can be used alone or in combination of two or more.

In addition to the above plasticizers, resins such as thermoplastic polyurethane resins and polyvinyl acetate can be used as plasticizers. 4. Other In the vinyl chloride resin composition of the present invention, if necessary,
Synthetic resins compatible with vinyl chloride resins, for example, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, chlorinated polyethylene, and the like can be blended. In addition, known resin additives usually blended in a synthetic resin for molding, for example, a heat stabilizer, a stabilizing aid, a lubricant,
Various additives such as an ultraviolet absorber, a flame retardant, an antistatic agent, a fungicide / antifungal agent, and a coloring agent can be blended.

Examples of the heat stabilizer include metal soaps such as barium stearate, zinc stearate and calcium stearate; tin-based stabilizers such as dibutyltin dilaurate, dibutyltin malate, and organic tin mercaptide; tribasic lead sulfate; Lead-based stabilizers such as dibasic lead phthalate, chelators such as triphenyl phosphite and dioctylphenyl phosphite, phenol derivatives such as hindered phenol, β-diketone compounds such as dibenzoylmethane, methoxybenzoyl and benzoylmethane. can give. These heat stabilizers can be used alone or in combination of two or more. Heat stabilizer is vinyl chloride resin 1
The total amount can be 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, per 100 parts by weight.

In addition, epoxy plasticizers, such as epoxidized soybean oil, epoxidized linseed oil, and liquid epoxy resin, which also function as a plasticizer, can be used as the heat stabilizer. The epoxy-based plasticizer can be added in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin. Examples of the lubricant include various lubricants such as fatty acid-based lubricant, fatty acid amide-based lubricant, ester-based lubricant, polyethylene wax, and liquid paraffin. The lubricant can be added in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the vinyl chloride resin.

Examples of the ultraviolet absorber include various ultraviolet absorbers such as benzotriazole, benzophenone, salicylate, hydroquinone, and cyanoacrylate, and these may be used alone or in combination of two or more. be able to. The ultraviolet absorber is used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin.
Parts by weight, preferably 0.5 to 3 parts by weight.

Examples of the flame retardant include antimony trioxide, zinc borate, barium metaborate, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium aluminate, red phosphorus, zinc stannate, zinc hydroxystannate, and molybdenum. And ammonium polyphosphate. The flame retardant can be added in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the antistatic agent include polyoxyethylene alkylamine, polyglycol ether, p
-Sodium styrene sulfonate. The antistatic agent is used in an amount of 0.1 to 100 parts by weight of the vinyl chloride resin.
It can be added in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight. Examples of the antibacterial and antifungal agents include phenol ether, calcium phosphate-silver, quaternary ammonium salts, pyridine, benzimidazole, haloalkylthio, triazine, and iodine antifungal agents. The antibacterial and fungicide is used in an amount of 0.05 to 2 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the vinyl chloride resin.
1.5 parts by weight can be added.

Examples of the coloring agent include phthalocyanine blue, phthalocyanine green, Hansa Yellow, Alizarin Lake, titanium oxide, zinc white, permanent red, quinacridone, carbon black and the like. These colorants can be used alone or in combination of two or more. In order to mix various additives and the like with the vinyl chloride resin, the respective required amounts are weighed, and a ribbon blender, a super mixer, a Banbury mixer and other conventionally known mixing machines and mixers may be used.

The vinyl chloride resin composition thus obtained can be formed into a film by a method known per se, for example, a calender molding method, a melt extrusion molding method (T-die method,
A conventionally known method such as an inflation method or a solution flow drawing method may be used. The thickness of the film is
0.05 to 0.6 mm is preferable, and 0.07 to 0.5 m
m is more preferable. If the thickness is less than 0.05 mm, wrinkles are likely to occur when the film is wound, and if the thickness is more than 0.6 mm, the appearance may be adversely affected.

The vinyl chloride resin film or sheet of the present invention may have a fine uneven pattern (texture pattern) on at least one surface.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments, but the present invention is not limited to the following examples unless it exceeds the gist. <Production of film made of vinyl chloride resin> A composition having the composition shown in Table 1 was stirred and mixed with a super mixer for 10 minutes, and then kneaded with a calender roll having a surface temperature of 180 ° C for 5 minutes to form a film having a thickness of 0.1 mm. A 1 mm vinyl chloride resin film was produced. <Composition analysis of acrylic copolymer> After performing qualitative analysis of the composition by pyrolysis gas chromatography mass spectrometry, quantitative analysis is performed by pyrolysis gas chromatography to analyze the composition (configuration) of the acrylic copolymer. The results are shown in Table-2.

The measuring apparatus and measuring conditions used in the above analysis are as follows. Pyrolysis gas chromatography mass spectrometer: GCMS-QP5050 manufactured by Shimadzu Corporation
A Pyrolysis furnace: PYR4A 550 ° C Carrier gas: He Pyrolysis gas chromatography Equipment: GC14BXC-R5A manufactured by Shimadzu Corporation Pyrolysis furnace: PYR4A 550 ° C Carrier gas: He <Evaluation of film> Film performance by the following method Was evaluated, and the results are shown in Table 1. Initial appearance The appearance of the film was visually observed.

The evaluation criteria are as follows. …: No gel-like substance such as fish eye on the surface and no roughness. Δ: A gel-like material such as fish eye or rough surface. ×: A gel-like substance such as fisheye on the surface and rough. Temperature Sensitivity of Film Using the films prepared in Examples and Comparative Examples, the tensile elastic modulus as the hardness of the film was determined by a method according to JIS K-7127. However, the test condition is that the test speed is 50 mm
/ Min, the test piece is a No. 4 type test piece, the distance between the grips of the test apparatus is 40 mm, the evaluation temperature is 10 ° C,
Two conditions of 35 ° C. were set.

The tensile elastic modulus ratio (10 ° C./35° C.) under the two conditions of 10 ° C. and 35 ° C. was determined and used as an index of the temperature sensitivity of the film. In addition, the smaller the ratio of the tensile modulus, the lower the temperature-sensitive film.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

As apparent from the above embodiments, the present invention has the following effects, and its utility value is extremely large. (1) Molded articles such as films obtained by using the vinyl chloride resin composition of the present invention hardly cause a difference in hardness even in an environment where a temperature difference occurs. Accordingly, it is not necessary to change the processing conditions, and the workability can be improved.

(2) A molded article such as a film obtained by using the vinyl chloride resin composition of the present invention hardly causes a difference in hardness even in an environment where a temperature difference is generated. Can be unified, and it can respond to simplification of inventory management in the market.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Keiji Tanaka 2nd Iwatsuka-cho, Iwatsuka-cho, Nakamura-ku, Nagoya-shi, Aichi F-term (reference) 4F071 AA22X AA24 AA31 AA31X AA42 AA43 AC10 AC15 AE04 AH03 AH04 AH06 AH19 BC01 4J002 BD04W BD05W BD06W BD07W BD08W BD09W BG03X CD003 CD163 CF003 EH096 EH146 EW046 EW056 FD023 FD026 GC00 GG00 GL00

Claims (3)

[Claims] 1. A plasticizer of 15 to 100 parts by weight, methyl methacrylate 2 based on 100 parts by weight of a vinyl chloride resin.
0-60% by weight, acrylate 10-60% by weight
And a vinyl chloride resin composition containing 10 to 200 parts by weight of a copolymer containing 1 to 20% by weight of a styrene monomer as a constituent. 2. The vinyl chloride resin composition according to claim 1, wherein the amount of the plasticizer is 20 to 40 parts by weight. 3. A film or sheet obtained by molding the vinyl chloride resin composition according to claim 1 or 2.