JPH08100156A - Tacky sheet - Google Patents

Abstract

PURPOSE: To prepare a tacky sheet whose primer coat layer is a resin layer consisting essentially of a PP resin or a specific modified acrylic acid ester, excellent in adhesiveness, retaining property, curved face-attaching ability, etc., even if the coating amount of a tacky agent is small and useful for label, seal and sticker, etc. CONSTITUTION: This tacky sheet is obtained by laminating (A) a surface substrate (e.g. film, paper or sheet), (B) an under coat layer, (C) a tacky agent layer and (D) a releasing sheep, and the component B is formed of a resin layer consisting essentially of a PP resin or an acrylic acid ester copolymer modified with an alkyleneimine compound. Furthermore, the component C is preferably composed of a copolymer obtained from 50-85wt.% of butyl acrylate, 10-40wt.% of a 6-18C alkyl ester of (meth)acrylic acid, 0.1-3wt.% of an ethylenic unsaturated carboxylic acid-containing monomer and 1-10wt.% of other monomer copolymerizable therewith and a tackiness providing agent.

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, and more particularly to an excellent pressure-sensitive adhesive sheet which exhibits sufficient pressure-sensitive adhesive performance even when the amount of pressure-sensitive adhesive applied is small.

[0002]

2. Description of the Related Art Adhesive sheets are used as labels, stickers, stickers, patches, etc. for a wide range of purposes such as commercial use, office use and household use. This adhesive sheet is generally constructed by laminating a surface base material, an adhesive and a release sheet. Paper, film, synthetic paper, metal foil, etc. are used for the surface base material, and high-density paper such as glassine paper for the release sheet, release sheet base paper such as clay-coated paper and poly-laminate paper, and silicone compounds and fluorine compounds. The one coated with the release agent is used. In addition, there are solvent-type adhesives, emulsion-type adhesives, hot-melt-type adhesives, etc. as the pressure-sensitive adhesives, but in recent years, emulsion-type pressure-sensitive adhesives have become very popular from the viewpoint of disaster prevention and occupational health. Came.

However, the emulsion type pressure-sensitive adhesive tends to be inferior to the solvent-type pressure-sensitive adhesive in the basic pressure-sensitive adhesive performance required for the pressure-sensitive adhesive, such as pressure-sensitive adhesive force, adhesive force and cohesive force. Therefore, when producing a high-quality pressure-sensitive adhesive sheet, the emulsion-type pressure-sensitive adhesive needs to be coated in a larger amount than the solvent-type pressure-sensitive adhesive. The coating amount of a general emulsion-type pressure-sensitive adhesive is about 22 to 27 g / m ² . In addition, when using a paper base material such as high-quality paper, kraft paper, art paper, or cast paper as the surface base material, there is a problem that the adhesive may not penetrate the paper base material and may not exhibit sufficient adhesive performance. is there.

[0004]

In view of the above situation, the present invention provides sufficient adhesive performance even when the amount of the adhesive applied is small and improves the adhesion between the surface substrate and the adhesive. (EN) An adhesive sheet which is excellent in workability and quality characteristics without leaving an adhesive on the adherend.

[0005]

The present invention relates to a pressure-sensitive adhesive sheet comprising a surface substrate, an undercoat layer, a pressure-sensitive adhesive layer, and a release sheet laminated together, the resin having a polypropylene resin as a main component. A pressure-sensitive adhesive sheet comprising a layer or a resin layer containing an acrylic acid ester copolymer modified with an alkyleneimine compound as a main component.

[0006]

The surface substrate constituting the pressure-sensitive adhesive sheet of the present invention includes, for example, cellophane, polyethylene, polypropylene,
Films such as soft polyvinyl chloride, hard polyvinyl chloride, polyester, fine paper, art paper, coated paper, cast paper, foil paper, kraft paper, polyethylene laminated paper, impregnated paper, vapor-deposited paper, water-soluble paper, etc. A sheet of metal, metal foil, synthetic paper, etc. coated or impregnated with an undercoating agent consisting of a resin containing polypropylene resin as a main component or a resin containing an acrylic acid ester copolymer modified with an alkyleneimine compound as a main component. Need to use. Incidentally, the polypropylene resin used in the present invention includes HYTEC E manufactured by Toho Chemical Industry Co., Ltd.
-433N, HYTEC P-5060 (brand name), Mitsui Petrochemical Co., Ltd. HT-121 (brand name), etc. can be mentioned.

The method for producing the polypropylene resin used as the undercoating agent is not particularly limited, and a polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method or a suspension polymerization method may be appropriately adopted. it can. Further, a thickener, a wetting agent, a leveling agent, a defoaming agent, a cross-linking agent, a pigment and the like may be appropriately added to the polypropylene resin used as the undercoating agent.

The acrylate copolymer modified with the alkyleneimine compound used in the present invention includes (meth) acrylic acid, cinnamic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid and monoalkylmalein. A monomer containing one or more kinds of carboxyl groups selected from acids, monoalkyl itaconic acid, monoalkyl fumaric acid and the like, and (meth) acrylamide, N-methylol (meth) acrylamide, 2-hydroxyethyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, t-butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth)
Acrylate, (meth) acrylonitrile, styrene,
Copolymerized with one or more monomers selected from α-methylstyrene, vinyl acetate, vinyl propionate, (meth) acrolein, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. The copolymer is ethyleneimine, propyleneimine, butyleneimine, N- (2-aminoethyl) aziridine, N- (3-aminopropyl) aziridine, N-
(2-aminopropyl) propyleneimine and the like are reacted.

The method for producing the copolymer for the undercoating agent is not particularly limited, and a polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method or a suspension polymerization method can be adopted. .

The monomer concentration during polymerization is usually 20 to
70% by weight, preferably about 30 to 60% by weight is suitable. Examples of the polymerization initiator used during the polymerization include persulfates such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2 ′.
-Azo compounds such as azobis (2,4-dimethylvaleronitrile), hydrogen peroxide, benzoyl peroxide,
Peroxides such as di-t-butyl peroxide, lauryl peroxide, ammonium persulfate and sodium sulfite,
Examples thereof include so-called redox type polymerization initiators which are combined with acidic sodium sulfite and the like. The amount of the above-mentioned polymerization initiator used is usually 0.
It is desirable that the amount is 2 to 2% by weight, and more preferably about 0.3 to 1% by weight. Further, as a chain transfer agent added during the polymerization, alkyl mercaptans such as octyl mercaptan, nonyl mercaptan, decyl mercaptan, dodecyl mercaptan, octyl thioglycolate, nonyl thioglycolate, thioglycolic acid-2-
Thioglycolates such as ethylhexyl and β-mercaptopropionate-2-ethylhexyl, 2,4
-Diphenyl-4-methyl-1-pentene, 1-methyl-4-isopropylidene-1-cyclohexene and the like can be mentioned. In particular, thioglycolic acid esters,
2,4-diphenyl-4-methyl-1-pentene, 1-
When methyl-4-isopropylidene-1-cyclohexene or the like is used, the copolymer obtained has a low odor, which is preferable.

The amount of the chain transfer agent used is adjusted in the range of 0.001 to 3% by weight based on the total monomers to be polymerized.
The polymerization reaction is usually at room temperature to 200 ° C., preferably 40 to 1
It is carried out under a temperature condition of 20 ° C. for about 2 to 8 hours. Further, the amination reaction with the alkyleneimine compound can be obtained, for example, by mixing and stirring the copolymer and the alkyleneimine under a temperature condition of 40 to 150 ° C, preferably 50 to 100 ° C. Further, a thickener, a wetting agent, a leveling agent, a defoaming agent, a cross-linking agent, a pigment and the like may be appropriately added to the undercoating copolymer.

The method of coating or impregnating the surface coating with the coating liquid for undercoating agent is, for example, an air knife coater,
Devices such as a roll coater, a gravure coater, a bar coater, a blade coater, a rod blade coater, a lip coater, a curtain coater, and various size press coaters are used. The coating amount of the undercoating agent is 0.1 to ²⁰ g / m ^{2 on} a dry weight basis, and more preferably 0.5 to 10 g.
It is adjusted in the range of / m ² .

The pressure-sensitive adhesive in the present invention is not particularly limited, but if an acrylic copolymer obtained by copolymerizing the following specific monomers with a tackifier added is used, However, even if the amount of the adhesive applied is considerably low, the adhesive performance is not deteriorated, which is desirable. (A) Butyl acrylate: 50 to 85% by weight (b) (Meth) acrylic acid alkyl ester monomer (alkyl group having 6 to 18 carbon atoms): 10 to 40% by weight (c) Ethylenically unsaturated carvone Acid-containing monomer: 0.1 to 3% by weight (d) Other monomer copolymerizable with these monomers: 1 to 10% by weight

It is preferable to use butyl acrylate as a main component as a monomer constituting the pressure-sensitive adhesive because the wettability with respect to various adherends is improved and the adhesion performance is remarkably improved.
By the way, if butyl acrylate is less than 50% by weight, the adhesive force and adhesive force are poor, and if it exceeds 85% by weight, the cohesive force of the adhesive becomes insufficient and the performance as an adhesive sheet may be deteriorated.

Next, as the (meth) acrylic acid alkyl ester monomer (alkyl group having 6 to 18 carbon atoms), for example, hexyl (meth) acrylic acid, octyl (meth) acrylic acid, (meth) acrylic acid- 2-ethylhexyl,
Stearyl (meth) acrylate and the like can be mentioned. The proportion of these monomers in the copolymer is 10 to
It is copolymerized in the range of 40% by weight. By the way, 10% by weight
If it is less than 40% by weight, on the other hand, if it exceeds 40% by weight, the adhesive force or cohesive force becomes insufficient, and the performance as a pressure-sensitive adhesive sheet is likely to deteriorate.

Examples of the ethylenically unsaturated carboxylic acid-containing monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, monoalkyl maleic acid, monoalkyl itaconic acid and monoalkyl fumaric acid. Can be mentioned. The proportion of these monomers in the copolymer is copolymerized in the range of 0.1 to 3% by weight. By the way, if it is less than 0.1% by weight, the adhesive strength is poor, and 3% by weight
If it exceeds, the storage stability of the pressure-sensitive adhesive sheet becomes insufficient and the performance as a pressure-sensitive adhesive sheet may be deteriorated.

Further, butyl acrylate, (meth) acrylic acid alkyl ester monomer (alkyl group having 6 carbon atoms)
To 18), and other monomers copolymerizable with the ethylenically unsaturated carboxylic acid-containing monomer include, for example, (meth)
Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, (meth)
Ethoxyethyl acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, styrene, divinylbenzene, ethylene, ( (Meth) acrylonitrile, (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N'-methylenebis (meth)
Acrylamide and the like can be mentioned, and the proportion of these monomers in the copolymer is copolymerized in the range of 1 to 10% by weight.

Among these other copolymerizable monomers, methyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and glycidyl (meth) acrylate are particularly preferable. , Divinylbenzene, (meth) acrylonitrile, (meth)
Acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide,
N, N′-methylenebis (meth) acrylamide and the like are preferable from the viewpoints of crosslinkability, control of glass transition temperature, adhesive performance and the like.

Further, a tackifier is added to the acrylic ester copolymer. The tackifier is an auxiliary agent that improves the adhesive force and the adhesive force, and the following can be exemplified. That is, rosin, polymerized rosin, partially hydrogenated rosin, glycerin ester rosin, fully hydrogenated rosin, pentaerythritol ester rosin, α-pinene polymer, β-
Pinene polymer, dipentene polymer, terpene-phenol, α-pinene-phenol copolymer, aliphatic hydrocarbon resin (olefin and diolefin polymer), cyclopentadiene resin, petroleum resin, phenol resin (alkylphenol and Modified phenol), alkylphenol-acetylene resin, styrene resin, xylene resin, coumarone indene resin, vinyltoluene-
It is an α-methylstyrene copolymer and the like. As the tackifier, at least one of the above is added. In addition, the mixing ratio is 10% by weight of the above acrylic ester copolymer.
It is 5 to 50 parts by weight with respect to 0 parts by weight. Incidentally, if it is less than 5 parts by weight, the effect of improving the adhesive force and the adhesive force is poor, and if it exceeds 50 parts by weight, the adhesive force and the adhesive force tend to decrease. The method for producing the above-mentioned copolymer for pressure-sensitive adhesive is not particularly limited, and it is produced by a method of emulsion polymerization in the presence of water, an emulsifier, a chain transfer agent, a polymerization initiator, a dispersant and the like.

The monomer concentration during the polymerization is usually 30 to
70% by weight, preferably about 40-60% by weight is suitable. Examples of the polymerization initiator used during the polymerization include persulfates such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2 ′.
-Azo compounds such as azobis (2,4-dimethylvaleronitrile), hydrogen peroxide, benzoyl peroxide,
Examples thereof include so-called redox-based polymerization initiators, which are composed of peroxides such as lauryl peroxide, and combinations of ammonium persulfate and sodium sulfite, acidic sodium sulfite, and the like. The amount of the above-mentioned polymerization initiator to be used is preferably 0.2 to 2% by weight, more preferably 0.3 to 1% by weight, based on the total amount of the monomers used for the usual polymerization. Further, as the chain transfer agent added during the polymerization, octyl mercaptan, nonyl mercaptan, decyl mercaptan,
Alkyl mercaptans such as dodecyl mercaptan, octyl thioglycolate, nonyl thioglycolate, 2-ethylhexyl thioglycolate, thioglycolic acid esters such as β-mercaptopropionate-2-ethylhexyl, 2,4-diphenyl-4 -Methyl-1-
Pentene, 1-methyl-4-isopropylidene-1-cyclohexene and the like can be mentioned. Particularly, thioglycolic acid esters, 2,4-diphenyl-4-methyl-1-pentene, 1-methyl-4-isopropylidene-
When 1-cyclohexene or the like is used, the resulting copolymer has a low odor, which is preferable. The amount of the chain transfer agent used is adjusted within the range of 0.001 to 3% by weight based on the total monomers to be polymerized. The polymerization reaction is usually performed under a temperature condition of 60 to 100 ° C. for about 2 to 8 hours. Further, a thickener, a wetting agent, a leveling agent, a defoaming agent and the like may be added to the copolymer for pressure-sensitive adhesive as appropriate.

Regarding the method of constructing the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive is applied on the surface of the release agent of the release sheet and dried to provide a pressure-sensitive adhesive layer according to a conventional method. The surface of the undercoating agent layer provided in the above is laminated and finished. As an apparatus for applying the pressure-sensitive adhesive, for example, a reverse roll coater, a knife coater, a bar coater, a slot die coater, an air knife coater, a reverse gravure coater, etc. are appropriately used. The amount of the adhesive applied is adjusted to a dry weight of 5 to 30 g / m ² , more preferably 7 to 20 g / m ² . By the way,
If it is less than 5 g / m ² , the adhesive performance of the resulting pressure-sensitive adhesive sheet will be insufficient, while if it exceeds 30 g / m ² , the pressure-sensitive adhesive may squeeze out or cause cohesive failure during peeling.

The pressure-sensitive adhesive sheet of the present invention obtained as described above exhibits sufficient pressure-sensitive adhesive performance even when the coating amount of the pressure-sensitive adhesive is small, and improves the adhesion between the surface base material and the pressure-sensitive adhesive to improve the adhesion. It is a pressure-sensitive adhesive sheet having excellent workability and quality characteristics without leaving an adhesive on the body.

[0023]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
In addition, the coating amount, the number of parts, the ratio and the like in the examples are all shown by the solid content weight.

Example 1 [Preparation of Surface Substrate] On the back surface of cast paper (trade name: Mirror Coat Gold <73> / Shin Oji Paper Co., Ltd.),
Polypropylene resin as undercoat (trade name: HT-1
21 / Mitsui Petrochemical Industry Co., Ltd.) was applied by a bar coater so that the weight after drying was 1.0 g / m ^2, and dried to obtain a surface base material.

[Production of Adhesive] Emulsified Monomer Mixture [A]
Was prepared with the following formulation. 340 g of 2-ethylhexyl acrylate, 2 g of acrylic acid, methyl methacrylate 5
8 g, anionic emulsifier (trade name: Rebenol wz / Kao Corporation) 2 g, nonionic emulsifier (trade name: Emulgen 920 / Kao Corporation) 6 g, ion-exchanged water 1
A mixed solution consisting of 70 g was prepared.

Next, in a 2 liter four-necked flask equipped with a stirrer, a cooler, a dropping funnel, a nitrogen suction tube, and a thermometer, 240 g of ion-exchanged water and the anionic emulsifier (trade name: Rebenol wz / Kao Corporation) 1 g, 1 g of a nonionic emulsifier (trade name: Emulgen 920 / manufactured by Kao Corporation) and 0.8 g of potassium persulfate were charged, the temperature was raised to 70 ° C. while substituting with nitrogen, and then the emulsion monomer mixture [A ] 1/6 was dripped. When the polymerization reaction rate reached 90%, the remaining emulsified monomer mixture liquid [A] was added dropwise over 2 hours for polymerization. After the dropping was completed, the reaction was matured at 70 ° C. for 2 hours to complete the polymerization reaction. After aging, the contents of the flask were cooled to 30 ° C. Thickener to this adhesive copolymer,
Add defoamer, dispersant, etc., neutralize with ammonia water,
The pressure-sensitive adhesive (coating liquid) having a concentration of 55% and a viscosity of 4000 cps was finished.

[Preparation of Adhesive Sheet] A commercially available polyethylene laminate release paper (trade name: Separate 110 EPS Cream / manufactured by Honshu Paper Co., Ltd.) was coated with the above adhesive on a dry weight of 17 g / m ^2. After being coated with a reverse roll coater and dried, it was attached to the surface of the above surface base material coated with the undercoating agent to obtain an adhesive sheet.

Example 2 [Preparation of surface base material] A pulp slurry consisting of 30 parts of bleached softwood kraft pulp with a freeness of 500 ml and 70 parts of bleached hardwood kraft pulp was used in a pulp slurry of 1.3% rosin size, 5% filler and sulfuric acid. After adding 2% of each band to prepare the paper stock, use a Fourdrinier paper machine to produce 64 g of tsubo.
/ M ² papermaking, polypropylene resin (trade name: HYTEC P-5060 / Toho Chemical Industry Co., Ltd.) concentration of 3% coating solution, so that the coating amount is 40 g / m ² After coating with a press coater and drying, the paper was passed through a machine calender to obtain a surface base material having a paper moisture content of 6.5%.

[Production of adhesive] Emulsified monomer mixture liquid [B]
Was prepared with the following formulation. 276 g of butyl acrylate,
2-ethylhexyl acrylate 100 g, acrylic acid 4 g, methyl methacrylate 10 g, vinyl acetate 10 g,
Anion-type emulsifier (trade name: Rebenol wz / manufactured by Kao Corporation) 3 g, anion-type reactive emulsifier (trade name: Eleminor JS-2 / manufactured by Sanyo Kasei Co., Ltd.) 1.5
g, 1.5 g of a nonionic reactive emulsifier (trade name: ADEKA RIASOAP NE-10 / manufactured by Asahi Denka Co., Ltd.), and 170 g of ion-exchanged water were prepared.

Next, in a 2-liter four-necked flask equipped with a stirrer, a cooler, a dropping funnel, a nitrogen suction tube, and a thermometer, 240 g of ion-exchanged water and the anionic emulsifier (trade name: Rebenol wz / Kao Corporation) ) 1 g, anionic reactive emulsifier (trade name: Eleminol JS-2
/ Manufactured by Sanyo Chemical Industry Co., Ltd.) 0.5 g, nonionic reactive emulsifier (trade name: ADEKA RIASOAP NE-10 / manufactured by Asahi Denka Co., Ltd.) 0.5 g, potassium persulfate 0.8 g
Was charged, the temperature was raised to 70 ° C. while substituting with nitrogen, and then 1/6 of the emulsified monomer mixture liquid [B] was added dropwise. When the polymerization reaction rate reached 90%, the remaining emulsified monomer mixture liquid [B] was added dropwise over 2 hours for polymerization. After the dropping was completed, the reaction was matured at 70 ° C. for 2 hours to complete the polymerization reaction. After aging, the contents of the flask were cooled to 30 ° C. To 100 parts by weight of this adhesive copolymer, 15 parts by weight of a tackifier (trade name: Super Ester E-650 / Arakawa Chemical Industry Co., Ltd.) (polymerized rosin) was added, and after stirring, a thickener and an eraser were added. A foaming agent, a dispersant, etc. were added, and the mixture was neutralized with aqueous ammonia to obtain an adhesive (coating liquid) having a concentration of 50% and a viscosity of 5000 cps.

[Preparation of Adhesive Sheet] A commercially available glassine release paper (trade name: Separate 85 GPS Asagi / manufactured by Honshu Paper Co., Ltd.) was reversely coated on the release agent-coated surface so that the dry weight was 13 g / m ^2. After being coated with a roll coater and dried, it was attached to the surface of the above surface base material coated with the undercoating agent to obtain an adhesive sheet.

Example 3 [Preparation of surface substrate] On the back surface of cast paper (trade name: Mirror Coat Gold <73> / manufactured by Shin Oji Paper Co., Ltd.),
Polypropylene resin as undercoat (trade name: HYTE
CE-433N / manufactured by Toho Chemical Industry Co., Ltd.) was applied with a bar coater so that the dry weight was 1.5 g / m ² .
A surface base material was obtained by drying.

[Production of Adhesive] Emulsified Monomer Mixture [C]
Was prepared with the following formulation. Butyl acrylate 290g,
86 g of 2-ethylhexyl acrylate, acrylic acid 4
g, methyl methacrylate 10 g, vinyl acetate 10 g, anion type emulsifier (trade name: Rebenol wz / manufactured by Kao Corporation) 3 g, anion type reactive emulsifier (trade name: Eleminol JS-2 / manufactured by Sanyo Kasei Co., Ltd.) 1 0.5 g,
Nonionic reactive emulsifier (trade name: ADEKA REASOAP N
E-10 / Asahi Denka Kogyo Co., Ltd.) 1.5 g, ion-exchanged water 170 g mixed solution.

Next, in a 2-liter four-necked flask equipped with a stirrer, a cooler, a dropping funnel, a nitrogen suction tube, and a thermometer, 240 g of ion-exchanged water and the anionic emulsifier (trade name: Rebenol wz / Kao Corporation) ) 1 g, anionic reactive emulsifier (trade name: Eleminol JS-2
/ Sanyo Kasei Co., Ltd.) 0.5 g, nonionic reactive emulsifier (trade name: ADEKA RIASOAP NE-10 / Asahi Denka Co., Ltd.) 0.5 g, potassium persulfate 0.8 g
Was charged, the temperature was raised to 70 ° C. while substituting with nitrogen, and then 1/6 of the emulsified monomer mixture liquid [C] was added dropwise. When the polymerization reaction rate reached 90%, the remaining emulsified monomer mixture liquid [C] was added dropwise over 2 hours for polymerization. After the dropping was completed, the reaction was matured at 70 ° C. for 2 hours to complete the polymerization reaction. After aging, the contents of the flask were cooled to 30 ° C. To 100 parts by weight of this adhesive copolymer, 17 parts by weight of a tackifier (trade name: Super Ester E-650 / Arakawa Chemical Industry Co., Ltd.) (polymerized rosin) was added, and after stirring, a thickening agent and a quenching agent were added. A foaming agent, a dispersant, etc. were added, and the mixture was neutralized with aqueous ammonia to obtain an adhesive (coating liquid) having a concentration of 45% and a viscosity of 4000 cps.

[Preparation of Adhesive Sheet] Commercially available polyethylene laminated release paper (trade name: Separate 110 EPS
Cream / manufactured by Honshu Paper Co., Ltd.), the above adhesive is applied to the release agent coated surface with a reverse roll coater so that the dry weight is 10 g / m ² , dried, and then laminated with the undercoating agent coated surface of the above surface substrate. To obtain an adhesive sheet.

Example 4 In Example 3, the monomer composition of the pressure-sensitive adhesive was changed to 240 g of butyl acrylate and 140 g of 2-ethylhexyl acrylate.
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that g, acrylic acid 8 g, methyl methacrylate 6 g, and vinyl acetate 6 g were used.

Example 5 In Example 3, the monomer composition of the adhesive was 320 g of butyl acrylate and 60% of 2-ethylhexyl acrylate.
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that g, acrylic acid 2 g, methyl methacrylate 10 g, and vinyl acetate 8 g were used.

Example 6 In Example 3, a tackifier (trade name: Super Ester E-65 was added to 100 parts by weight of the copolymer for adhesives).
A pressure-sensitive adhesive sheet was manufactured in the same manner as in Example 3 except that 8 parts by weight of 0 / made by Arakawa Chemical Industry Co., Ltd. (polymerized rosin) was added.

Example 7 In Example 3, a tackifier (trade name: Super Ester E-65 was added to 100 parts by weight of the copolymer for adhesives).
A pressure-sensitive adhesive sheet was manufactured in the same manner as in Example 3 except that 40 parts by weight of 0 / made by Arakawa Chemical Industry Co., Ltd. (polymerized rosin) was added.

Example 8 A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 except that the tackifier was partially hydrogenated rosin (trade name: ester gum SE-50 / manufactured by Arakawa Chemical Industry Co., Ltd.). Manufactured.

Example 9 In Example 3, the tackifier was petroleum resin (trade name: K).
E-756B / manufactured by Arakawa Chemical Industry Co., Ltd.), and a pressure-sensitive adhesive sheet was manufactured in the same manner as in Example 3.

Example 10 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that the tackifier was an aliphatic hydrocarbon resin (trade name: KZ-815 / manufactured by Kyowa Chemical Industry Co., Ltd.). did.

Example 11 In Example 3, polypropylene resin (trade name: HY
TEC E-433N / manufactured by Toho Chemical Co., Ltd.) 3 g /
except for m ² coating was produced a pressure-sensitive adhesive sheet in the same manner as in Example 3.

Example 12 In Example 3, polypropylene resin (trade name: HY
TEC E-433N / manufactured by Toho Chemical Co., Ltd.) 8 g /
except for m ² coating was produced a pressure-sensitive adhesive sheet in the same manner as in Example 3.

Example 13 In Example 3, polypropylene resin (trade name: HY
12 g of TEC E-433N / manufactured by Toho Chemical Co., Ltd.)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that the pressure-sensitive adhesive sheet was applied in an amount of / m ² .

Example 14 [Production of Acrylic Ester Copolymer Modified with Alkyleneimine Compound] A resin was synthesized with the following formulation in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing tube. did. Isopropyl alcohol: 21 parts Toluene: 49 parts Methacrylic acid: 2.4 parts Methyl methacrylate: 27.6 parts

The above composition was charged into a flask and heated to 80 ° C. while blowing nitrogen gas. To this, 0.14 parts of azobisbutyronitrile was added in several batches over 7.5 hours while maintaining the liquid temperature at 80 ° C., and after the final addition, it was kept at 80 ° C. for another hour. And it cooled to room temperature and obtained the solution of the copolymer containing a carboxyl group. Next, 1.3 parts of ethyleneimine was added dropwise to the above flask over 10 minutes. After 1 hour from the completion of the dropping, the temperature was raised to 75 ° C., and the temperature was maintained at the same temperature for 4 hours.
A distillation apparatus was set in the one-necked flask and heated under reduced pressure to remove isopropyl alcohol and unreacted ethyleneimine out of the system. Finally, the non-volatile content was adjusted to 10% with toluene to obtain an undercoating agent coating liquid.

[Preparation of Surface Substrate] Cast paper (trade name:
Mirror coat gold <73> / manufactured by Shin Oji Paper Co., Ltd.), and an acrylic acid ester copolymer modified with an alkyleneimine compound as a primer is applied on a bar coater to give a dry weight of 1.0 g / m ^2. It was applied and dried to obtain a surface base material.

[Preparation of Adhesive Sheet] Commercially available polyethylene laminated release paper (trade name: Separate 110 EPS
Cream / manufactured by Honshu Paper Co., Ltd.), the same adhesive as in Example 1 was applied by a reverse roll coater to a dry weight of 17 g / m ^2, and after drying, an undercoating agent for the above surface substrate. An adhesive sheet was obtained by sticking to the coated surface.

Example 15 [Preparation of surface base material] A pulp slurry of 30 parts of bleached softwood kraft pulp (NBKP) and 70 parts of bleached hardwood kraft pulp (LBKP) with a freeness of 500 ml was added to a pulp slurry of 1.3% rosin size per pulp. Filler 5%, sulfuric acid band 2
% Respectively to prepare a paper stock, which was then paper-made using a Fourdrinier paper machine so as to have a weight of 64 g / m ^2, and an acrylic acid ester copolymer modified with an alkyleneimine compound (trade name: Polyment SK-1000 / manufactured by Nippon Shokubai Co., Ltd.) containing a coating liquid having a concentration of 3% and a coating liquid amount of 40 g /
It was coated with a size press coater so as to have a surface area of m ² , dried, and then passed through a machine calender to obtain a surface base material having a paper moisture content of 6.5%.

[Preparation of Adhesive Sheet] A commercially available glassine release paper (trade name: Separate 85 GPS Asagi / manufactured by Honshu Paper Co., Ltd.) was coated with the same adhesive as in Example 2 at a dry weight of 13 g / m ² . After applying with a reverse roll coater and drying so that it was adhered to the above surface substrate, an adhesive sheet was obtained.

Example 16 [Preparation of surface substrate] On the back surface of cast paper (trade name: Mirror Coat Gold <73> / manufactured by Shin Oji Paper Co., Ltd.),
Acrylic ester copolymer modified with alkyleneimine compound as a primer (trade name: Polyment KX-C
K500 / manufactured by Nippon Shokubai Co., Ltd.) was applied with a bar coater to a dry weight of 1.5 g / m ² and dried to obtain a surface base material.

[Preparation of Adhesive Sheet] Commercially available polyethylene laminate release paper (trade name: Separate 110 EPS
Cream / manufactured by Honshu Paper Co., Ltd.), the same adhesive as in Example 3 was applied by a reverse roll coater so as to have a dry weight of 10 g / m ^2, and after drying, an undercoating agent for the above surface substrate. An adhesive sheet was obtained by sticking to the coated surface.

Example 17 In Example 3, the monomer composition of the pressure-sensitive adhesive was changed to 240 g of butyl acrylate and 140 g of 2-ethylhexyl acrylate.
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that g, acrylic acid 8 g, methyl methacrylate 6 g, and vinyl acetate 6 g were used.

Example 18 In Example 3, the monomer composition of the pressure-sensitive adhesive was changed to 320 g of butyl acrylate and 60% of 2-ethylhexyl acrylate.
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that g, acrylic acid 2 g, methyl methacrylate 10 g, and vinyl acetate 8 g were used.

Example 19 In Example 3, a tackifier (trade name: Super Ester E-65 was added to 100 parts by weight of the copolymer for adhesives).
A pressure-sensitive adhesive sheet was manufactured in the same manner as in Example 3 except that 8 parts by weight of 0 / made by Arakawa Chemical Industry Co., Ltd. (polymerized rosin) was added.

Example 20 In Example 3, a tackifier (trade name: Super Ester E-65 was added to 100 parts by weight of the copolymer for adhesives).
A pressure-sensitive adhesive sheet was manufactured in the same manner as in Example 3 except that 40 parts by weight of 0 / made by Arakawa Chemical Industry Co., Ltd. (polymerized rosin) was added.

Example 21 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 3 except that the tackifier was partially hydrogenated rosin (trade name: ester gum SE-50 / manufactured by Arakawa Chemical Industry Co., Ltd.). Manufactured.

Example 22 In Example 3, the tackifier was petroleum resin (trade name: K).
E-756B / manufactured by Arakawa Chemical Industry Co., Ltd.), and a pressure-sensitive adhesive sheet was manufactured in the same manner as in Example 3.

Example 23 A pressure-sensitive adhesive sheet was manufactured in the same manner as in Example 3 except that the tackifier was an aliphatic hydrocarbon resin (trade name: KZ-815 / manufactured by Kyowa Chemical Industry Co., Ltd.). did.

Example 24 In Example 3, an acrylate copolymer modified with an alkyleneimine compound (trade name: Polyment N
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that 3 g / m ^{2 of} K-200 PM / manufactured by Nippon Shokubai Co., Ltd. was applied.

Example 25 Example 3 was modified with an alkyleneimine compound.
Acrylic ester copolymer (trade name: Polyment N
K-350 / Nippon Shokubai Co., Ltd.) 8 g / m ²Applied
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except for the above.

Example 26 In Example 3, an acrylate copolymer modified with an alkyleneimine compound (trade name: Polyment N) was used.
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that 12 g / m ^{2 of} K-307 / produced by Nippon Shokubai Co., Ltd. was applied.

Comparative Example 1 Example 1 was repeated except that the pressure-sensitive adhesive was applied by a reverse roll coater so that the dry weight was 25 g / m ² , and the adhesive was bonded to a surface base material having no undercoat layer. A pressure-sensitive adhesive sheet was produced in the same manner as in.

Comparative Example 2 Example 1 was repeated except that the pressure-sensitive adhesive was applied by a reverse roll coater so that the dry weight was 10 g / m ^2, and the surface was coated with a surface base material having no undercoat layer. A pressure-sensitive adhesive sheet was produced in the same manner as in.

Comparative Example 3 In Example 3, a copolymer emulsion consisting of 27% by weight of ethylene, 70% by weight of vinyl chloride and 3% by weight of acrylamide was applied as a primer on the back surface of the surface substrate.
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that it was dried.

The pressure-sensitive adhesive sheets thus obtained were evaluated as follows, and the obtained results are shown in Tables 1 and 2.

[Adhesive force] A load (g / 25) when peeled at an angle of 180 ° at a tensile speed of 300 mm / min by an Instron type tensile tester in accordance with JIS Z 0237.
mm) was measured. (Adherend: polyethylene)

[Holding power] According to JIS Z 0237,
The time to fall was measured. (time)

[Applicability to curved surface attachment] A small piece (20 mm in length, 16 mm in width) of the pressure-sensitive adhesive sheet obtained in each example was attached to a polyethylene pipe (outer diameter: 13 mm), and the floating from both ends after one day was visually determined. did. ⊚: No uplifting ○: There is some uplifting, but there is no problem in practical use Δ: There is considerable uplifting, which is a problem in practical use ×: Fully uplifting

[Comprehensive Evaluation] The performance of the pressure-sensitive adhesive sheet of the present invention was evaluated by combining the above evaluations. ⊚: Very good performance ◯: Excellent performance Δ: Slightly insufficient, but at a level where there is no practical problem ×: Insufficient, practical problem Is a level

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Effect] As is apparent from the examples, the pressure-sensitive adhesive sheet obtained in the present invention had high adhesive strength and holding power even when the amount of the pressure-sensitive adhesive applied was small, and was excellent in curved surface sticking suitability.

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Claims (3)

[Claims] 1. A pressure-sensitive adhesive sheet comprising a surface base material, an undercoating agent layer, a pressure-sensitive adhesive layer, and a release sheet laminated together, wherein the undercoating agent layer comprises a resin layer containing a polypropylene resin as a main component. Adhesive sheet. 2. A pressure-sensitive adhesive sheet comprising a surface base material, an undercoating agent layer, a pressure-sensitive adhesive layer, and a release sheet laminated together, wherein the undercoating agent layer comprises an acrylic acid ester copolymer modified with an alkyleneimine compound as a main component. A pressure-sensitive adhesive sheet comprising a resin layer containing 3. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is the following (a):
The pressure-sensitive adhesive sheet according to claim 1 or 2, comprising a copolymer having a monomer composition of to (d) and a tackifier. (A) Butyl acrylate: 50 to 85% by weight (b) (Meth) acrylic acid alkyl ester monomer (alkyl group having 6 to 18 carbon atoms): 10 to 40% by weight (c) Ethylenically unsaturated carvone Acid-containing monomer: 0.1 to 3% by weight (d) Other monomer copolymerizable with these monomers: 1 to 10% by weight