JPH10338847A - Pressure-sensitive adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sheet having good cuttability, good transfer to an application pressure-sensitive adhesive sheet and good anchor to a base sheet and desirable for decoration by selecting a pressure-sensitive adhesive sheet wherein the pressure-sensitive adhesive comprises a pressure-sensitive adhesive base polymer and a non-reactive release controlling agent having a specified structure in a specified ratio. SOLUTION: This sheet has a structure formed by laying a pressure-sensitive adhesive and release paper on one surface of a synthetic resin sheet. The pressure-sensitive adhesive comprises 100 pts.wt. base polymer and 0.005-3 pts.wt. non-reactive release controlling agent represented by the formula. For use for decoration, the synthetic resin sheet is desirably a vinyl chloride resin sheet. The pressure-sensitive adhesive base polymer is desirably especially an acrylic pressure-sensitive adhesive having good weathering resistance. The non-reactive release controlling agent is added to the pressure-sensitive adhesive layer in order to prevent the cut surfaces from uniting again with the elapse of time when the pressure-sensitive adhesive layer is cut. The release paper is prepared by laying a silicone resin or a release controlling agent to one surface of base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive sheet which is excellent in cuttability by a cutting machine and excellent in transferability to an application pressure-sensitive adhesive sheet and is suitable for indoor or outdoor decoration or marking.

[0002]

2. Description of the Related Art Conventionally, an adhesive layer has been laminated on one surface of a synthetic resin sheet such as a vinyl chloride resin sheet, an acrylic resin sheet, a fluorine resin sheet, etc., which is transparent, translucent and opaque mainly containing a pigment. 2. Description of the Related Art A decorative pressure-sensitive adhesive sheet is known. This decorative adhesive sheet is used to apply a decorative effect to the material to be decorated by using an adhesive layer, and to exert a decorative effect by the color and pattern on the surface side. It is used in the field of display such as types, public notices and signs, and the field of fleet marking such as vehicle decoration.

The above-mentioned conventional decorative adhesive sheet has a structure in which an adhesive layer and a release paper are sequentially laminated on the back surface of a synthetic resin sheet, and this is usually provided by a computer-controlled cutting machine or manually. After cutting into shapes such as figures and letters, peeling off unnecessary parts in advance and leaving only necessary parts, it is further transferred to an application adhesive sheet and transferred to the adherend to be decorated It is constructed by the method.

[0004] However, the conventional decorative adhesive sheet has a problem that a necessary part is removed in a scrap removing operation after cutting by a cutting machine or a manual operation. A method of changing to a heavy peeling type and increasing the peeling strength between the adhesive and the release paper has been adopted.

In addition to the above, Japanese Patent Application Laid-Open No. 2-84476
In the gazette, in the dynamic peel resistance between the pressure-sensitive adhesive layer and the release layer of the release paper, by giving a speed dependence by limiting the peel strength at low speed peeling and high speed peeling respectively to a specific range, There is disclosed a pressure-sensitive adhesive sheet for a cutting machine in which "turn-up" generated near a cut portion is prevented.

However, the method of increasing the peeling strength has a problem that the transferability is remarkably lowered when only the necessary portion is transferred to the application adhesive sheet after the unnecessary portion is peeled in advance. Further, Japanese Patent Application Laid-Open No. 2-84
The pressure-sensitive adhesive sheet for a cutting machine described in Japanese Patent No. 476 does not completely solve the same problem.

The present invention has been made to solve the above problems, and as a result of diligent studies, it has been found that by adding a specific amount of a non-reactive release control agent to an adhesive, the pressure-sensitive adhesive sheet is cut. This is achieved by finding that the non-reactive release control agent covers the cut surface of the pressure-sensitive adhesive and suppresses re-adhesion of the cut surface of the pressure-sensitive adhesive.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a pressure-sensitive adhesive sheet which is excellent in cutability and transferability to an application pressure-sensitive adhesive sheet, and which has a good anchoring property to a substrate sheet and is suitable for decoration. It is to provide.

[0009]

Means for Solving the Problems The pressure-sensitive adhesive sheet of the present invention comprises:
An adhesive and a release paper are laminated on one side of a synthetic resin sheet in this order, wherein the adhesive is 100 parts by weight of an adhesive base polymer and a non-reactive release control agent 0 represented by the following formula: It is characterized by comprising 0.005 to 3 parts by weight.

Hereinafter, the present invention will be described in detail. Synthetic Resin Sheet As the synthetic resin sheet used in the present invention, a general synthetic resin sheet base material conventionally used for a decorative sheet, a marking film or the like can be used, and is not particularly limited. Examples of such a synthetic resin sheet include, for example, a vinyl chloride resin sheet, an acrylic resin sheet, a urethane resin sheet, a fluorine resin sheet, and the like, but for decorative applications requiring flexibility and weather resistance. As such, a vinyl chloride resin sheet is preferable.

The above synthetic resin sheet may be added with a plasticizer, an ultraviolet absorber, a heat stabilizer, a filler, a coloring agent and the like in order to improve various performances.

The plasticizer is added for the purpose of imparting flexibility to the synthetic resin sheet. For example, phthalic acid-based plasticizers such as dioctyl phthalate, diisononyl phthalate, octyldecyl phthalate and diisodecyl phthalate are used. Adipic acid-based plasticizers such as di-2-ethylhexyl adipate, diisononyl adipate, and diisodecyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate, tricresyl phosphate,
Trixylyl phosphate, tributyl phosphate, tri-phosphate
2-ethylhexyl, octyl diphenyl phosphate, chlorinated paraffin, chlorinated fatty acid esters, and the like are included.

Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based and cyanoacrylate-based ultraviolet absorbers.

Examples of the heat stabilizer include metal soap heat stabilizers, organotin heat stabilizers, lead heat stabilizers, antimony heat stabilizers, and nonmetal heat stabilizers.
Examples of the metal soap-based heat stabilizer include Pb, C
Metal soaps composed of d, Ba, Zn, Ca and the like and stearic acid, lauric acid, ricinoleic acid, naphthenic acid, 2-ethylhexoic acid and the like, and specifically, Cd
/ Ba heat stabilizer, Ba / Zn heat stabilizer, Ca / Zn
Heat stabilizer, Ba / Pb heat stabilizer, Cd / Ba / Zn
Heat stabilizers, Cd / Mg / Zn heat stabilizers, and the like.

Examples of the above-mentioned organotin heat stabilizer include dibutyltin dilaurate, dibutyltin maleate, dibutyltin mercaptide and the like. Examples of the lead-based heat stabilizer include, for example, lead white, basic lead sulfite, tribasic lead sulfate, dibasic lead phosphite, dibasic lead phthalate, tribasic lead maleate, silica gel coprecipitated. Examples include lead silicate, dibasic lead stearate, lead stearate and the like.

The non-metallic heat stabilizer includes, for example,
(I) Trialkyl phosphites such as tributyl phosphite, triisooctyl phosphite, triisodecyl phosphite, and trilauryl phosphite, monoisooctyl diphenyl phosphite, monoisodecyl diphenyl phosphite, diisooctyl monophenyl phosphite Phosphites such as alkylaryl phosphites such as phytite, triphenyl phosphite, tris (p-phenylphenyl) phosphite, and tris (o-cyclohexylphenyl) phosphite; (ii) acetylacetone, benzoylacetone, and benzoylpropionylmethane; β-diketone and the like.

Examples of the filler include calcium carbonate, talc (basic magnesium silicate), kaolin (aluminum silicate), silica, and titanium oxide.

Examples of the colorant include organic pigments such as azo, phthalocyanine, sulene and dye lakes, oxides, molybdate chromate, sulfide / selenide, ferrocyanide, etc. And inorganic pigments.

As a method for producing the synthetic resin sheet, any conventionally known method is employed. In the case of a vinyl chloride resin, for example, a vinyl chloride resin sol is obtained by dispersing constituent components in an organic solvent, and A sol-casting method in which the composition is heated and cured after coating and drying on paper, and a calendering method in which the constituent components are heated and melted to form a sheet are exemplified. Examples of the organic solvent serving as a dispersion medium used in the sol casting method include, for example, toluene, xylene, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, and the like.
Examples of commercially available products include “Solvesso” (manufactured by Mitsubishi Chemical Corporation).

Although the thickness of the synthetic resin sheet is not particularly limited, it is usually about 30 to 200 μm, more preferably about 40 to 100 μm. If the thickness of the synthetic resin sheet is too thin, it will lose its stiffness and the workability when used as a decorative sheet or a marking film may be reduced. In some cases, the ability to adhere to an adherend may be reduced.

Adhesive The adhesive used in the present invention comprises 100 parts by weight of an adhesive base polymer and 0.005 to 3 parts by weight of a non-reactive release control agent having a specific structure.

Pressure-sensitive adhesive base polymer Examples of the pressure-sensitive adhesive base polymer include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives such as natural rubber-based and synthetic rubber-based, urethane-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. In particular, an acrylic pressure-sensitive adhesive is preferably used because it has good weather resistance.

Hereinafter, the case of an acrylic pressure-sensitive adhesive will be described in detail. The acrylic pressure-sensitive adhesive is mainly composed of an acrylic copolymer, and is preferably cross-linked by a cross-linking agent.

The acrylic copolymer is usually obtained by copolymerizing a mixed monomer mainly composed of an alkyl (meth) acrylate and a polar group-containing vinyl monomer.

The alkyl (meth) acrylate is preferably an alkyl (meth) acrylate having 4 to 14 carbon atoms in the alkyl group. Since the homopolymer has a glass transition temperature of -50 ° C. or lower, it can be used as a main component. Thus, the balance of pressure-sensitive adhesiveness and shear strength of the resulting acrylic pressure-sensitive adhesive can be kept high. Examples of the alkyl (meth) acrylate include n-butyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n
-Octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate,
Examples include isononyl (meth) acrylate and lauryl (meth) acrylate, which may be used alone or in combination of two or more.

When the content of the alkyl (meth) acrylate is small, the cohesive strength is increased and sufficient pressure-sensitive adhesiveness is hardly obtained, and when the content is large, the cohesive strength is reduced and it is difficult to obtain sufficient shear strength. , In the mixed monomer, preferably 50 to 98% by weight, more preferably 70 to 98% by weight.
~ 95% by weight.

The polar group-containing vinyl monomer includes:
For example, carboxyl group-containing vinyl monomers such as (meth) acrylic acid, itaconic acid, crotonic acid, (anhydrous) maleic acid, fumaric acid, carboxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl Hydroxyl-containing vinyl monomers such as (meth) acrylate, caprolactone modified (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate, (meth) acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl Lauriloractam, (meth) acryloylmorpholine, (meth) acrylamide, dimethyl (meth) acrylamide, N-
Methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl ( Examples thereof include nitrogen-containing vinyl monomers such as meth) acrylate, and these may be used alone or in combination of two or more.

When the content of the polar group-containing vinyl monomer is small, the cohesive strength is reduced and it is difficult to obtain a shear strength, and when the content is too large, the cohesive strength is increased and it is difficult to obtain pressure-sensitive adhesiveness. , Preferably 2-5
0% by weight, more preferably 5 to 30% by weight.

The above-mentioned mixed monomers include alkyl (meth)
In addition to acrylates and polar group-containing vinyl monomers,
Other vinyl monomers are contained and may be copolymerized,
For example, vinyl acetate, vinyl propionate, styrene,
Isobornyl (meth) acrylate;

As the content of the other vinyl monomer increases, the cohesive strength increases and it becomes difficult to obtain sufficient pressure-sensitive adhesiveness. Therefore, the total amount of the vinyl monomer and the polar group-containing vinyl monomer is preferably 50% by weight in the mixed monomer. %, More preferably 30% by weight or less.

Examples of the method for copolymerizing the above-mentioned mixed monomer include all polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization, and include (meth) acrylic acid and hydroxyalkyl (meth) acrylate. Solution polymerization is preferred because the carboxyl group-containing vinyl monomer has good copolymerizability, is easy to control the coating viscosity, and is easily mixed with a crosslinking agent, a tackifying resin and the like.

In the above solution polymerization, a thermal polymerization initiator is generally used. Examples of the thermal polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide and cyclohexanone peroxide, isobutyryl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and P-chloro. Diacyl peroxides such as benzoyl peroxide, diisopropylbenzene hydroperoxide, hydroperoxides such as t-butyl hydroperoxide,
Dialkyl peroxides such as 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 1,3-bis- (t-butylperoxyisopropyl) benzene, and di-t-butyl peroxide , 1,1-di-
(T-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di- (t-butylperoxy)
Peroxyketals such as cyclohexane, t-butylperoxypivalate, t-butylperoxy-2-
Alkyl peresters such as ethylhexanoate and t-butylperoxyisobutyrate, di-2-ethylhexylperoxydicarbonate, bis- (4-t-
In addition to organic peroxides such as percarbonates such as butylcyclohexyl) peroxydicarbonate,
2'-azobis-isobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis-1-cyclohexanecarbo Nitrile, dimethyl-
Examples include azobis compounds such as 2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis- (2-aminopropane) dihydrochloride.

When the acrylic copolymer is obtained, a chain transfer agent may be added to the mixed monomer for the purpose of suppressing the dispersion of the polymerization reaction and appropriately controlling the molecular weight.
Examples of the chain transfer agent include n-dodecyl mercaptan, 2-mercaptoethanol, β-mercaptopropionic acid, octyl β-mercaptopropionate, β
-Methoxybutyl mercaptopropionate, trimethylolpropane tris (β-thiopropionate), butyl thioglycolate, thiol compounds such as propanethiols, butanethiols, thiophosphites, and halogen compounds such as carbon tetrachloride. Is mentioned.

The weight average molecular weight (Mw) of the acrylic copolymer obtained above is measured as a standard polystyrene equivalent molecular weight by a gel permeation chromatography (GPC) method. Specifically, the acrylic copolymer before cross-linking is referred to as tetrahydrofuran (hereinafter referred to as “THF”).
To make a 0.5-1.0% by weight solution,
It is separated by a gel packed column using F as a dispersion medium, and is determined from the relationship between the elution time and the refractive index of the elution solution.

When the weight-average molecular weight (Mw) of the acrylic copolymer is small, sufficient cohesive strength is difficult to obtain, and when the weight-average molecular weight (Mw) is large, the viscosity of the pressure-sensitive adhesive solution is increased and the coating property is reduced. ~ 1,000,000 is preferred.

The crosslinking agent used for crosslinking the acrylic copolymer varies depending on the type of the polar group-containing vinyl monomer copolymerized in the acrylic copolymer. When a carboxyl group-containing vinyl monomer is copolymerized as a polar group-containing vinyl monomer, an epoxy-based cross-linking agent, an aziridine-based cross-linking agent, or the like is suitably used. It is preferably used.

As the epoxy-based crosslinking agent, for example,
Examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Examples of the aziridine-based crosslinking agent include N, N-hexamethylene-1,6-bis (1 -Aziridinecarboxamide) and the like, and as the isocyanate-based crosslinking agent, for example, tolylene diisocyanate (TDI),
Naphthylene-1,5-diisocyanate, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), xylene diisocyanate (XD
I) and trimethylolpropane modified TDI.

When the amount of the cross-linking agent is small, it is difficult to obtain a sufficient degree of cross-linking. For this reason, it is difficult to obtain a sufficient shear strength with a decrease in cohesive force. Is impaired, and it becomes difficult to obtain sufficient pressure-sensitive adhesiveness. For this reason, the addition amount is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the solid content of the acrylic copolymer.
3 parts by weight.

If the gel fraction of the acrylic pressure-sensitive adhesive is too low, no cohesive strength can be obtained, and particularly when the acrylic pressure-sensitive adhesive is applied to a curved plate or the like, peeling or swelling tends to occur. Therefore, it is preferable to crosslink so as to be 40 to 65% by weight.

Other additives may be added to the acrylic pressure-sensitive adhesive as needed as long as other physical properties are not reduced, and examples thereof include a tackifier resin and a filler.

As the tackifying resin, for example, C5
-Based and C9-based petroleum resins, rosin resins, rosin ester resins, terpene resins, terpene phenol resins, cumarone-indene resins, disproportionated rosin resins, disproportionated rosin ester resins, polymerized rosin resins, polymerized rosin ester resins, or a mixture thereof. All tackifying resins such as hydrogenated products are included. The above tackifier resins may be used alone or in combination of two or more.

Since the tackifying resin is an uncrosslinked component in the pressure-sensitive adhesive, the cohesive strength is reduced when the amount of the added resin is large, and sufficient shear strength cannot be obtained. For this reason, the addition amount is preferably 30 parts by weight or less based on 100 parts by weight of the acrylic copolymer.

Examples of the filler include calcium carbonate, talc (basic magnesium silicate), kaolin (aluminum silicate), silica and the like.

If the glass transition temperature of the acrylic pressure-sensitive adhesive is low, a sticky feeling may be felt during construction in summer and the workability may decrease. If the glass transition temperature is high, the adhesiveness in winter may decrease. 5 ° C. is preferred.

Non-Reactive Release Control Agent The pressure-sensitive adhesive layer used in the present invention comprises the above-mentioned pressure-sensitive adhesive base polymer and a non-reactive release control agent. The non-reactive release control agent is added to the pressure-sensitive adhesive layer for the purpose of preventing the cut surface from re-adhering over time when the pressure-sensitive adhesive layer is cut, and is represented by the following formula: No.

[0046]

Embedded image

Commercial products of the non-reactive release control agent include "Shin-Etsu Silicone X-92-128" (manufactured by Shin-Etsu Chemical Co., Ltd.).

The amount of the non-reactive release control agent added is
When the amount is too small, the re-adhesion preventing performance of the adhesive cannot be sufficiently obtained, and when the amount is too large, the adhesive strength and the adhesiveness (anchor property) between the adhesive layer and the synthetic resin sheet are reduced. 0.005 to 3 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the base polymer.
To 1 part by weight, more preferably 0.02 to 0.05 part by weight.

When the thickness of the pressure-sensitive adhesive layer is small, sufficient adhesion to an adherend cannot be obtained, and when the thickness is large, cohesive failure occurs in the side stick or the pressure-sensitive adhesive layer.
μm is preferred.

Release Paper The release paper used in the present invention is a paper in which a release agent is laminated on at least one surface of a normal base material. Addition of a release control agent or a reactive release control agent, and adjustment to give a desired peel strength can be given.

Examples of the base material include paper base materials such as high-quality paper, kraft paper, and glassine paper; woven fabric; nonwoven fabric; synthetic fiber; net; plastic film; Things.

The silicone resin in the release agent must be applied to a substrate as a mixture with the above-mentioned non-reactive or reactive release control agent, dried, and then cured by heating. Examples of the curing catalyst to be used include a platinum-based catalyst, a tin-based catalyst, and the like. As a commercially available product of the platinum-based catalyst, a product number “CAT-PL-50” is used.
T "(manufactured by Shin-Etsu Chemical Co., Ltd.).

The method of applying the release agent to the substrate is as follows.
For example, all the usual liquid material coating methods can be mentioned, for example, a gravure coater, a Meyer bar coater, a multi-stage roll, an air knife coater and the like.

The heating conditions for curing are as follows:
The temperature is preferably 60 ° C. or more at 0 ° C., 40 seconds or more at 100 ° C., and 30 seconds or more at 120 ° C.

The thickness of the release agent layer is preferably 0.5 to 2 μm because if it is thin, it is difficult to obtain release performance, and if it is thick, the release agent layer tends to fall off due to poor curing.

If the total thickness of the release paper after laminating the release agent layer is too thin, it may be difficult to handle the entire sheet, and if it is too thick, the workability when peeling off the release paper may decrease. There is. Therefore, the thickness of the release paper is usually 80
To 300 μm, preferably 100 to 200 μm.

Method for Producing a Pressure-sensitive Adhesive Sheet The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer and release paper laminated on one surface of a synthetic resin sheet in this order. The method for producing the pressure-sensitive adhesive sheet is not particularly limited, and after applying a pressure-sensitive adhesive solution to one surface of a synthetic resin sheet, the pressure-sensitive adhesive layer may be laminated by drying, and then laminated with a release paper. Alternatively, after applying the pressure-sensitive adhesive solution to one side of the release paper, the pressure-sensitive adhesive layer may be dried and laminated with the surface of the pressure-sensitive adhesive layer and the synthetic resin sheet.

[0058]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following non-limiting examples. (Examples 1 to 4 and Comparative Examples 1 to 3) Synthetic resin sheet (vinyl chloride resin sheet) Vinyl chloride resin (manufactured by Kaneka Chemical Co., Ltd., trade name "PSH-1")
0 ") 100 parts by weight, adipic acid plasticizer (trade name" P-300 ", manufactured by Asahi Denka Co., Ltd.) 30 parts by weight, Ca / Zn heat stabilizer (trade name," MARK SC-3 ", manufactured by Asahi Denka Co., Ltd.)
4)) 5 parts by weight and 60 parts by weight of an organic solvent (manufactured by Mitsubishi Chemical Corporation, trade name "Solvesso") were uniformly mixed, coated on process paper, dried, and then heated and cured at 200 ° C. for 5 minutes. A vinyl chloride resin sheet having a thickness of 50 μm was obtained.

In a separable flask equipped with an acrylic pressure-sensitive adhesive reflux condenser, a thermometer and a stirrer, 60 parts by weight of n-butyl acrylate, 28 parts by weight of 2-ethylhexyl acrylate, and acrylic acid
7 parts by weight, 2-hydroxyethyl methacrylate 0.3
Parts by weight and 0.01 parts by weight of n-dodecyl mercaptan were added together with 80 parts by weight of ethyl acetate, and the temperature was raised to reflux while purging with nitrogen gas and held. Next, a 5% by weight solution of benzoyl peroxide in ethyl acetate was added.
First, 0.1 part by weight, 0.1 part by weight after 30 minutes, 0.2 part by weight after 1 hour and 30 minutes, and then 3 parts by weight
After the time, 0.8 parts by weight was added dropwise over 30 minutes, and after the entire amount was added, the mixture was polymerized for further 5 hours to obtain a solution of an acrylic copolymer. The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of each of the acrylic copolymers were determined by gel permeation chromatography (GPC) to find that Mw = 700,000 and Mw / Mn = 3.1. there were.

Next, an isocyanate-based cross-linking agent (trade name “Coronate L-50” manufactured by Nippon Polyurethane Co., Ltd.) is added to 1 part by weight of the solid content based on 100 parts by weight of the solid content of the acrylic copolymer. Other than Comparative Example 1, "Shin-Etsu Silicone X" was used as a non-reactive release control agent.
-92-128 "or" Shin-Etsu Silicone KS-38 "
"00" (both manufactured by Shin-Etsu Chemical Co., Ltd.) was added according to the compounding amount shown in Table 1 to obtain an acrylic pressure-sensitive adhesive.

[0061] as a release paper release paper, using "WSLP-70" (Fujimori Kogyo Co., Ltd.). Adhesive sheet Each acrylic adhesive solution was applied to the release paper so that the thickness after drying became 30 μm, and dried in an oven at 120 ° C. for 5 minutes. Each of the pressure-sensitive adhesive sheets was obtained by bonding under heating at a temperature of ° C.

(Evaluation of Examples and Comparative Examples) The pressure-sensitive adhesive sheets obtained in the above-mentioned Examples and Comparative Examples were cut by the methods described below, the transferability of application pressure-sensitive adhesive sheets, and the vinyl chloride resin sheet and pressure-sensitive adhesive. The anchor properties between the layers were each measured.

The adhesive sheet obtained was cut into a cutting machine “CG-4”.
Using "5" (manufactured by Mimaki), four sets of characters "Sekisui Chemical" in 30 mm x 30 mm size were cut in a total of 24 characters, and after 1 minute, 30 minutes, and 3 hours, debris was removed and required. The cutability was evaluated by determining the number of remaining characters.

Application Adhesive Sheet Transferability With respect to the obtained adhesive sheet, the application adhesive sheet (manufactured by Sekisui Chemical Co., Ltd., product number “AP217”) was sufficiently pressed with a squeegee on the 12 characters remaining on the release paper due to scrap removal. Then, the state of transfer at the time of peeling after standing for 10 minutes was evaluated in the following five stages. [Evaluation criteria] 5: Transfer all 12 characters 4: Transfer 11 characters or not transfer dots etc. 3: Transfer 7 to 10 characters 2: Transfer 1 to 6 characters 1: Do not transfer characters

Between the vinyl chloride resin sheet and the pressure-sensitive adhesive layer
Prepare two sheets of adhesive sheet obtained with anchor property of
g by reciprocating the pressure roller once.
After leaving at room temperature for 1 minute, a T-peel test was performed at a peeling speed of 300 mm / min using a tensile tester, and the anchor property between the vinyl chloride resin sheet and the adhesive layer was visually observed. Was evaluated. [Evaluation Criteria] 3: The adhesive did not peel off from the vinyl chloride resin sheet. 2: The pressure-sensitive adhesive was separated from the vinyl chloride resin sheet in a dot-like manner. 1: More than half of the adhesive was peeled off from the vinyl chloride resin sheet.

[0066]

[Table 1]

[0067]

According to the present invention, since the pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive base polymer and a non-reactive release control agent, it is cut at a high speed by a computer-controlled cutting machine or the like, and then left as it is. Also, re-adhesion of the pressure-sensitive adhesive cut surface does not easily occur, the workability of scrap removal is good, and the transferability to the application pressure-sensitive adhesive sheet is also good. Further, by controlling the addition amount of the non-reactive release control agent within a specific range, the anchor property between the pressure-sensitive adhesive layer and the synthetic resin sheet is also good.

Claims (1)

[Claims] 1. A pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive and a release paper are laminated in this order on one side of a synthetic resin sheet, wherein the pressure-sensitive adhesive is 100 parts by weight of a pressure-sensitive adhesive base polymer and non-reactive release represented by the following formula: Control agent 0.005-
An adhesive sheet comprising 3 parts by weight. Embedded image