JP2002105268A - Vinyl chloride resin composition for calender molding and tacky adhesive sheet made of vinyl chloride resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for a soft vinyl chloride resin film improving glossiness of a surface without bad influence upon a tacky adhesive, film hardening with the elapse of time, nor an increase in a cost, and also provide a tacky adhesive sheet made of the vinyl chloride resin and having a base layer molded using this resin composition. SOLUTION: The vinyl chloride resin composition for calender molding is prepared by compounding a polyester plasticizer and a phthalic acid plasticizer to a vinyl chloride resin, preferably in the ratio of 1:2.2-1:0.08. The vinyl chloride resin tacky adhesive sheet is formed by arranging of the tacky adhesive layer on one surface of a base layer made of a soft vinyl chloride resin which is prepared by calender molding of the vinyl chloride resin composition.

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 for calender molding and a pressure-sensitive adhesive sheet made of the vinyl chloride resin having a base material layer formed using the resin composition, and particularly to an outdoor and indoor advertising sticker. The present invention relates to a vinyl chloride resin composition for calender molding suitably used for the production of a decorative vinyl chloride resin pressure-sensitive adhesive sheet used as a stick, a display sticker, a decoration sticker, and the like, and a pressure-sensitive adhesive sheet thereof. The pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive film, and the pressure-sensitive adhesive sheet used for the above-mentioned applications is generally often referred to as a marking film.

[0002]

2. Description of the Related Art Such a pressure-sensitive adhesive sheet made of a vinyl chloride resin for decoration is generally made of a soft vinyl chloride resin film as a base material, and pigments are kneaded with the base material according to the purpose, or the base material is colored. After printing and painting, apply a suitable pressure-sensitive adhesive (pressure-sensitive adhesive) to one side according to the application and purpose, to form a pressure-sensitive adhesive layer, and if necessary, to protect the pressure-sensitive adhesive layer It is configured by bonding a release material such as release paper. When used, the release material is peeled off and affixed to a predetermined location for use.

This decorative vinyl chloride resin adhesive sheet is often used outdoors, for example, advertising stickers used for signboards, advertising towers, shutters, show windows, etc .; vehicles such as automobiles and motorcycles; Decorative stripe stickers used for ships such as motorboats; used for display stickers used for traffic signs, road signs, information boards, etc. Conventionally, a soft vinyl chloride resin film used as a base material of a decorative vinyl chloride resin adhesive sheet has been manufactured by a calendering method or a casting method, but in general, the calendering method is used because of its superiority in productivity and cost. It was often adopted. When used as such a decorative sheet, the appearance quality is regarded as important, and the glossiness of the product surface in particular has a great influence on the appearance impression. However, the soft vinyl chloride resin film produced by the calender method tends to have a lower glossiness than that of the casting method, and is therefore expensive even in many applications such as outdoor and indoor signboards. Regardless, sheets created by the casting method were often used. Examples of the method for improving the glossiness of the soft vinyl chloride resin film by the calender method include a method of blending a phosphate ester-based surfactant and a recovered ferrite compound (see Japanese Patent Application Laid-Open No. 60-38451) and a method for improving the glossiness. A method of blending a plasticizer composed of a terpolymer (Table 4)
No. 502644) has been proposed. But,
The use of a base material layer obtained from a composition to which a plasticizer comprising a special terpolymer as described in JP-T-Hei 4-502644 has been added naturally leads to an increase in the cost of a decorative sheet which is strongly demanded for a low price. However, it has been difficult to adopt the method from a practical viewpoint.

[0004]

In addition, according to the study of the present inventor, as described in JP-A-60-38451, a resin composition containing a surfactant and a specific recovered compound is disclosed. When a pressure-sensitive adhesive layer is laminated on a base material layer and used as a pressure-sensitive adhesive sheet, these compounds may bleed into the pressure-sensitive adhesive layer, resulting in a problem of adhesion inhibition and film curing with time.

The present invention has been made in view of the above-mentioned problems of the conventional pressure-sensitive adhesive sheet made of a vinyl chloride resin for decoration, and provides a resin composition for a soft vinyl chloride resin film used as a base layer.
Provide a resin composition capable of improving the glossiness of the surface without causing adverse effects on the pressure-sensitive adhesive or film curing over time, and increase in cost, and having a base material layer formed using the resin composition. An object is to provide a pressure-sensitive adhesive sheet made of a vinyl chloride resin.

[0006]

In order to achieve the above object, according to the first aspect of the present invention, a polyester plasticizer and a phthalic plasticizer are blended as a plasticizer with a vinyl chloride resin. Provided is a vinyl chloride resin composition for calender molding. Further, in the invention according to claim 2, the blending ratio of the two plasticizers is polyester: phthalic acid = 1: 1.
The present invention provides a vinyl chloride resin composition for calendar molding, wherein the composition is 2.2 to 1: 0.08. The invention according to claim 3 is:
A vinyl chloride resin pressure-sensitive adhesive sheet comprising a soft vinyl chloride resin base material layer formed by calendering the calender-forming vinyl chloride resin composition according to claim 1 or 2 and a pressure-sensitive adhesive layer provided on one surface thereof. Hereinafter, the present invention will be described in more detail.

[0007] The vinyl chloride resin composition for calender molding of the present invention is obtained by blending a polyester plasticizer and a phthalic acid plasticizer as a plasticizer with the vinyl chloride resin. Usually, it has the property of being excellent in weather resistance when used for a vinyl chloride resin and being excellent in non-migration to the pressure-sensitive adhesive layer over time, and a phthalic acid plasticizer is generally used for a vinyl chloride resin. In this case, the film has excellent fluidity, exhibits high glossiness of the film, and has characteristics of providing high appearance quality without bank marks.

As the phthalic acid plasticizer, for example,
Diethyl phthalate, dibutyl phthalate, di-2-phthalate
Conventionally known compounds such as ethylhexyl and diisononyl phthalate may be used, and these may be used alone or in combination with a plurality of phthalic acid-based plasticizers. Examples of the polyester plasticizer include, for example, conventionally known polyester plasticizers of adipic acid such as dibutyl adipate, di-n-hexyl adipate, and isononyl adipate. May be blended in
A plurality of polyester plasticizers may be blended. The molecular weight of the polyester plasticizer is not particularly limited, but usually about 900 to 1100 is used.

The mixing ratio of these two plasticizers is preferably such that the phthalic acid-based plasticizer is 0.08 to 2.2 parts by weight per 1 part by weight of the polyester-based plasticizer. If the amount of the phthalic acid-based plasticizer is less than 0.08 part by weight, it tends to be difficult to improve the surface gloss and provide a film having a high appearance without bank marks. When the base material layer is obtained by calender molding by blending with a vinyl resin, there is a tendency that an adverse effect on the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet and film hardening over time are easily caused. In any case outside the range of 0.08 to 2.2 parts by weight, the soft vinyl chloride resin film used as the base material layer constituting the pressure-sensitive adhesive sheet made of the vinyl chloride resin does not bring about cost increase or deterioration of weather resistance. In addition, it is difficult to provide a good surface gloss and to eliminate the adverse effect on the pressure-sensitive adhesive and the fear of film curing over time.

The amount of the phthalic acid-based plasticizer and the polyester-based plasticizer is usually 10 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin.
Parts by weight.

The above-mentioned vinyl chloride resin composition may further comprise a polyester plasticizer and a phthalic acid plasticizer as essential components, if necessary, as long as the object of the invention is not hindered.
Coloring agents, heat stabilizers, ultraviolet absorbers, inorganic or organic fillers, softeners, plasticizers, surfactants, antioxidants (antiaging agents), lubricants, antistatic agents, antiblocking agents,
One or more of various additives such as an organic solvent may be added.

The pigments and dyes used as the colorant are not particularly limited, but include, for example, azo based carbon black, titanium white, lake C and the like, phthalocyanine blue such as phthalocyanine blue and phthalocyanine green, and And dye lakes such as rhodamine lake, quinacrine red, cadmium yellow, and chromium vermillion.

These pigments and dyes may be used alone or in combination of two or more, but it is preferable to select and use pigments and dyes having excellent weather resistance. Examples of the heat stabilizer include epoxidized compounds such as epoxidized soybean oil and epoxidized fatty acid esters, and organic stabilizers such as tributyl phosphite, Ba / Zn stabilizers, and Ca / Zn stabilizers. Metal-based stabilizers are exemplified. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers are often used because they have high weather resistance and transparency.

The pressure-sensitive adhesive sheet made of a vinyl chloride resin of the present invention comprises:
An adhesive layer is provided on one surface of a soft vinyl chloride resin base material layer obtained by calendering the above-mentioned vinyl chloride resin composition for calender molding. The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer constituting the vinyl chloride resin pressure-sensitive adhesive sheet of the present invention is not particularly limited, for example,
Acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, polyvinyl ether-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and the like, among which acrylic-based pressure-sensitive adhesives are preferred because of their excellent weather resistance, heat resistance, and transparency Used.

The acrylic pressure-sensitive adhesive is not particularly limited, but, for example, the alkyl group has 4 to 1 carbon atoms.
2, a homopolymer of an alkyl (meth) acrylate monomer or a copolymer of alkyl (meth) acrylate monomers, or a copolymer of an alkyl (meth) acrylate monomer and a polymerizable monomer copolymerizable with the alkyl (meth) acrylate monomer. It is mainly composed of a copolymer or the like. Incidentally, (meth) acrylate referred to in the present invention means acrylate or methacrylate.

The alkyl (meth) acrylate monomer having 4 to 12 carbon atoms in the alkyl group is not particularly limited. For example, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Isooctyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, and the like are included.

These alkyl (meth) acrylate monomers may be used alone or in combination of two or more, but the tackiness (tack) of the resulting pressure-sensitive adhesive is
In order to improve the balance between the adhesive strength and the cohesive strength, the glass transition temperature (Tg) of the homopolymer should be -50.
The main component is an alkyl (meth) acrylate monomer whose temperature is lower than or equal to ° C., and the number of carbon atoms of an alkyl group such as methyl (meth) acrylate or ethyl (meth) acrylate is 1 to 1.
It is preferable to use together with the alkyl (meth) acrylate monomer of No. 3.

The polymerizable monomer copolymerizable with the alkyl (meth) acrylate monomer is not particularly limited, but includes, for example, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, Carboxyl group-containing monomers such as itaconic acid, and 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl acrylate, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, and caprolactone-modified (meth) acrylate And a hydroxyl group-containing monomer. These polymerizable monomers may be used alone or in combination of two or more.

The form of the pressure-sensitive adhesive used in the present invention including the above-mentioned acrylic pressure-sensitive adhesive is not particularly limited.
For example, any form such as a solvent-type adhesive, an emulsion-type adhesive, a hot-melt-type adhesive, and a monomer-type or oligomer-type adhesive capable of performing bulk polymerization such as photopolymerization by irradiation with ultraviolet light may be used. Further, the pressure-sensitive adhesive may be of a cross-linked type or a non-cross-linked type.

The above-mentioned vinyl chloride resin composition for calender molding may be, for example, a three-roll type roll calender, a four-roll calender (four L-types, four inverted L-types, four Z-types, four tilted Z-type rolls). By a calendering method using an appropriate roll calender such as a calender, for example, it is formed into a film for a soft vinyl chloride resin base material layer or the like constituting the vinyl chloride resin pressure-sensitive adhesive sheet of the present invention.

The thickness of the pressure-sensitive adhesive layer formed by using the above-mentioned pressure-sensitive adhesive after drying is not particularly limited.
It is preferably from 50 to 50 μm. If the thickness of the pressure-sensitive adhesive layer after drying is less than 20 μm, the resulting pressure-sensitive adhesive sheet may have insufficient tackiness or tackiness, and conversely, the thickness of the pressure-sensitive adhesive layer after drying may be 50 μm. If it exceeds, the pressure-sensitive adhesive layer (glue) tends to ooze out from the end of the obtained pressure-sensitive adhesive sheet, dust adheres to the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer causes cohesive failure when the pressure-sensitive adhesive sheet is removed again after use, Adhesive residue may occur on the surface of the adherend.

In the pressure-sensitive adhesive sheet of the present invention, a release material is usually laminated and adhered to the pressure-sensitive adhesive layer. As the release material, for example, a release paper or release paper obtained by subjecting at least one surface of paper or a plastic film to a release treatment with a silicone resin-based release agent or a long-chain alkyl group pendant type graft polymer-based release agent or the like. Mold film and the like.

The method for producing the pressure-sensitive adhesive sheet of the present invention is not particularly limited. For example, a pressure-sensitive adhesive is directly applied to a film for a soft vinyl chloride resin base material layer using a usual coating roll to form the pressure-sensitive adhesive layer. Method, or applying a pressure-sensitive adhesive to the release-treated surface of the release material (process paper) so as to have a predetermined coating thickness by a reverse coating method, a hot melt coating method, or the like, and drying or cooling as necessary. After forming a pressure-sensitive adhesive layer having a predetermined thickness after drying through steps such as the above, laminating this pressure-sensitive adhesive layer and the other surface of the substrate layer and transferring the pressure-sensitive adhesive layer to the substrate layer side By the (transfer method), a desired pressure-sensitive adhesive sheet can be obtained.

[0024]

EXAMPLES (Example 1) A vinyl chloride resin composition was prepared, and a pressure-sensitive adhesive sheet formed by laminating a vinyl chloride resin film and a pressure-sensitive adhesive layer was prepared and evaluated by the following method. 2 parts by weight of epoxidized soybean oil, 1 part by weight of Ba-Zn stabilizer and 1 part by weight of a plasticizer shown in Table 1 are blended with 100 parts by weight of vinyl chloride resin (degree of polymerization 1050) to form a vinyl chloride resin composition. , 170 ° C heating calender roll (reverse L
(Using 4 rolls) and 0.08mm thick
Was prepared.

Next, an acrylic pressure-sensitive adhesive (SK133, manufactured by Soken Chemical Co., Ltd.) was placed on release paper treated on both sides with a polymer release agent.
5) 100 parts by weight and a crosslinking agent (M-5 manufactured by Soken Chemical Co., Ltd.)
A) 5 parts by weight, ultraviolet absorber (PYV manufactured by Asahi Denka Chemical Co., Ltd.)
A) 3 parts by weight of a pressure-sensitive adhesive composition mixed and stirred,
An adhesive layer having a thickness of 0 μm (dry thickness) was obtained. This pressure-sensitive adhesive layer with release paper and the above soft vinyl chloride resin film
The samples were laminated under heating at a temperature of ° C. to prepare a sample.

[0026]

[Table 1]

(Examples 2 to 5, Comparative Examples 1 to 3) Samples were prepared in the same manner as in Example 1 except that the compounding of the plasticizer was as shown in Table 1.

The samples obtained in the respective Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 2. <Evaluation method> Glossiness evaluation: gloss checker (IG-330, manufactured by HORIBA), measurement angle: 60 ° Evaluation of film hardness over time: Strength at 2% elongation was measured according to JIS Z 0237. The quality of the blank and the sample after 7 days at 60 ° C. were compared and indicated by the rate of increase. Incidentally, the higher the rate of increase, the higher the value of the film hardness over time.

Adhesive strength over time: The adhesive strength of the SP plate was measured according to JIS Z 0237. The quality of the blank and the sample after 7 days at 60 ° C. were compared and indicated by a reduction rate. Weather resistance: The degree of discoloration of the sample after 216 hours of accelerated exposure was visually evaluated using a super UV tester (manufactured by Daiplau Intes).

[0030]

[Table 2]

[0031]

The vinyl chloride resin composition for calender molding of the present invention is obtained by calender molding since a polyester plasticizer and a phthalic plasticizer are blended as a plasticizer with the vinyl chloride resin. The resulting film or sheet has a good surface gloss without deteriorating the weather resistance, and also has a practical effect that it can be provided at low cost without increasing the cost. When the mixing ratio of the two plasticizers is in a specific range, the above-described effects can be more reliably achieved.

The vinyl chloride resin pressure-sensitive adhesive sheet of the present invention has a soft vinyl chloride resin base layer obtained by calendering the above-described calender-forming vinyl chloride resin composition of the present invention. Is a pressure-sensitive adhesive sheet having a good balance of various properties, having a good surface glossiness without deteriorating weather resistance, and having no adverse effect on the pressure-sensitive adhesive or fear of film curing over time.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09J 7/02 C09J 7/02 Z

Claims (3)

[Claims] 1. A vinyl chloride resin composition for calender molding, wherein a polyester plasticizer and a phthalic acid plasticizer are blended as a plasticizer with a vinyl chloride resin. 2. A vinyl chloride resin composition for calender molding, wherein the mixing ratio of the two plasticizers is polyester: phthalic acid = 1: 2.2 to 1: 0.08. 3. A pressure-sensitive adhesive layer is provided on one surface of a soft vinyl chloride resin base material layer obtained by calendering the vinyl chloride resin composition for calendar molding according to claim 1 or 2. Adhesive sheet made of vinyl chloride resin.