KR101193705B1

KR101193705B1 - Releasable adhesive sheet, method for manufacturing same, and releasable adhesive sheet laminate

Info

Publication number: KR101193705B1
Application number: KR1020077021877A
Authority: KR
Inventors: 히사유키 타카야마; 타쿠야 테츠모토
Original assignee: 린텍 가부시키가이샤
Priority date: 2005-03-29
Filing date: 2006-03-27
Publication date: 2012-10-22
Also published as: TWI406924B; WO2006104235A1; KR20070116611A; JP4916435B2; CN101151341A; TW200702415A; JPWO2006104235A1; CN101151341B

Abstract

In the present invention, a pressure-sensitive adhesive containing a spherical pressure-sensitive adhesive and an emulsion-type binder pressure-sensitive adhesive is coated on one side of the base sheet to form a pressure-sensitive adhesive layer, wherein the spherical pressure-sensitive adhesive is 0.1 to 100 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer component. 0.1-7 mass with respect to 100 mass parts of solid content of a spherical adhesive to the spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer in the presence of 3 mass parts polyacrylic acid (A), or a spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer. The releasable adhesive sheet which is a spherical adhesive (B) obtained by adding negative polyacrylic acid is provided. The re-peelable pressure-sensitive adhesive sheet of the present invention is characterized by having a uniform adhesive force and a peeling force with little unevenness of adhesive force and peeling force due to light weight of the pressure.

Description

Releasable Adhesive Sheet, Manufacturing Method and Releasable Adhesive Sheet Laminate [RELEASABLE ADHESIVE SHEET, METHOD FOR MANUFACTURING SAME, AND RELEASABLE ADHESIVE SHEET LAMINATE}

The present invention provides a re-peelable pressure-sensitive adhesive sheet having a uniform adhesive force and a peel force with little unevenness of adhesive force and peeling force due to light weight of pressure, a manufacturing method thereof, and a re-peelable pressure-sensitive adhesive using a re-peelable pressure-sensitive adhesive sheet. It relates to a sheet laminate.

Recently, the fine spheres of the adhesive resin are arranged on the surface of the base sheet to be bonded to form an adhesive sheet, the surface of the enclosed fine spheres is affixed to another adhered surface, and then the adhesive sheet is peeled off if necessary, The adhesive sheet which can repeat the operation which affixes on a to-be-adhered surface again was discovered.

As for the adhesive sheet used for such a use, the adhesive layer which consists of a spherical adhesive was formed in one side of the base sheet with which the primer layer was apply | coated conventionally as desired. As such a pressure-sensitive adhesive sheet, for example, a re-peelable pressure-sensitive adhesive sheet using a spherical pressure-sensitive adhesive is proposed (see Japanese Patent Laid-Open No. 2-194079), and a re-peelable pressure-sensitive adhesive and A re-peelable pressure-sensitive adhesive sheet in which various compounds are mixed is proposed (see Japanese Patent Laid-Open No. 2004-137313).

However, in such an adhesive sheet, when pressure is added strongly, adhesive force may change or peeling force may increase. Specifically, for example, in the manufacture of a laminate of pressure-sensitive adhesive sheets, the pressure-sensitive adhesive sheet is faced to face the peelable surface of the pressure-sensitive adhesive sheet adjacent to the pressure-sensitive adhesive surface, and sequentially laminated to form a laminate of pressure-sensitive adhesive sheets, and with a cutting knife. When cutting to a predetermined size, a pressure is fixed and cut to the cutting portion in order to prevent the deviation from occurring in the cutting portion. In this case, in the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer, nonuniformity occurred in the adhesive force and the peeling force. In addition, when the adhesive sheet is wound in a roll shape and left to stand, the pressure added state is different in the portion close to the core of the roll and the portion near the outer side of the roll. Was doing.

That is, there existed a problem that the unevenness of the adhesive force and peeling force by the light weight of pressure was large, and the re peelable adhesive sheet which has uniform adhesive force and peeling force was hardly obtained.

In addition, when the adhesive layer of the conventional adhesive sheet is molded on a part of the surface of the base sheet, an adhesive is applied to the entire surface of the transfer roll of the roll coater, and then some adhesive is removed by a blade. The method of partially forming an adhesive layer on the roll surface and transferring it to a base material sheet is performed. In this case, when the adhesive is removed by the blade, the adhesive remains on the surface of the transfer roll without being completely removed, and the adhesive is applied to a portion where the adhesive layer is not needed, or even if the removal is sufficient, the separation of the adhesive is bad. It becomes difficult to apply | coat, such that it flows out on the roll surface from which the adhesive of the shape adhesive layer was removed, and it is difficult to make the width | variety of a strip | belt-shaped adhesive layer as set, or aggregates generate | occur | produce easily in an adhesive, and foam | bubble generate | occur | produces simultaneously. There was a problem that caused.

MEANS TO SOLVE THE PROBLEM This invention solves the said subject, The adhesive peeling adhesive sheet which has uniform adhesive force and peeling force with little unevenness of adhesive force and peeling force by the weight of pressure, and a pressure sensitive adhesive blade at the time of partial application to a roll surface By removing the adhesive, the separation of the pressure-sensitive adhesive is good, the width of the band-shaped pressure-sensitive adhesive layer can be prepared as set, and the aggregate hardly occurs in the pressure-sensitive adhesive, and at the same time, bubbles are hardly generated, and also have the above characteristics. An object of the present invention is to provide a method for producing a re-peelable pressure-sensitive adhesive sheet, and a re-peelable pressure-sensitive adhesive sheet laminate using the re-peelable pressure-sensitive adhesive sheet.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, as a result of earnestly examining, the adhesive layer apply | coated to the single side | surface of a base material sheet consists of the adhesive containing a spherical adhesive and an emulsion type binder adhesive, and also the spherical adhesive is ethylene Solid content of a spherical adhesive 100 to the spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer in presence of 0.1-3 mass parts polyacrylic acid with respect to 100 mass parts of series unsaturated monomer components, or the spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer. By making it the spherical adhesive obtained by adding 0.1-7 mass parts polyacrylic acid with respect to a mass part, it discovered that the said subject could be solved and came to complete this invention.

That is, in this invention, the adhesive containing a spherical adhesive and an emulsion binder adhesive is apply | coated to the single side | surface of a base material sheet, and the adhesion layer is formed, The said spherical adhesive is based on 100 mass parts of ethylenically unsaturated monomer components. 0.1-7 mass parts with respect to 100 mass parts of solid content of a spherical adhesive to the spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer in presence of 0.1-3 mass parts polyacrylic acid, or the spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer. It is a spherical adhesive obtained by adding polyacrylic acid, It is providing the re-peelable adhesive sheet characterized by the above-mentioned.

The present invention also provides a re-peelable pressure-sensitive adhesive sheet winding roll, wherein the pressure-sensitive adhesive sheet is wound in a roll shape.

Moreover, in this invention, the adhesive containing a spherical adhesive and an emulsion binder adhesive is partially apply | coated to the single side | surface of a base material sheet, and the adhesion layer is formed, The said spherical adhesive is 100 mass parts of ethylenically unsaturated monomer components. 0.1-7 with respect to 100 mass parts of solid content of a spherical adhesive to the spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer in presence of 0.1-3 mass parts of polyacrylic acid, or the spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer. It is a spherical adhesive obtained by adding a polyacrylic acid part by mass, to provide a re-peelable pressure-sensitive adhesive sheet.

In addition, the present invention provides a re-peelable pressure-sensitive adhesive sheet in the re-peelable pressure-sensitive adhesive sheet, wherein the pressure-sensitive adhesive is a pressure-sensitive adhesive having a coagulation rate of 5.0 mass% or less.

In the present invention, in the re-peelable pressure-sensitive adhesive sheet, the pressure-sensitive adhesive layer has an adhesive force of 1.0 N / 105 mm or more on the stainless steel plate, and the ratio of the adhesive force to the stainless steel plate and the adhesive force to the surface of the base sheet is 1: 0.2. It is providing the re-peelable adhesive sheet which is the range of -1: 1.

The present invention also provides a re-peelable pressure-sensitive adhesive sheet laminate, wherein a plurality of sheets of the re-peelable pressure-sensitive adhesive sheet are laminated.

Moreover, after this invention apply | coats the adhesive containing a spherical adhesive and an emulsion binder adhesive to the surface of an adhesive layer transfer metal roll, the applied adhesive is partially removed by a blade, and a strip | belt-shaped adhesive layer is formed. The method for producing a re-peelable pressure-sensitive adhesive sheet by transferring the band-shaped pressure-sensitive adhesive layer to one side of the base sheet, wherein the spherical pressure-sensitive adhesive is 0.1 to 3 parts by mass of polyacrylic acid based on 100 parts by mass of the ethylenically unsaturated monomer component. Spherical shape obtained by adding 0.1-7 mass parts polyacrylic acid with respect to 100 mass parts of solid content of a spherical adhesive to the spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer in presence or a spherical adhesive obtained by polymerizing an ethylenically unsaturated monomer. It is to provide a method for producing a re-peelable pressure-sensitive adhesive sheet, characterized in that the pressure-sensitive adhesive.

1 is a cross-sectional view illustrating an example of an apparatus for producing a re-peelable pressure-sensitive adhesive sheet of the present invention;

Fig. 2 is a perspective view of a rolled up releasable pressure-sensitive adhesive sheet of the present invention and a laminate of the re-peelable pressure-sensitive adhesive sheet of the present invention.

1: Base Sheet 2: Adhesive

3: adhesive layer transfer metal roll 4: adhesive layer

5: Band-shaped adhesive layer 6: Blade

7: pressure-sensitive adhesive layer pressure roll 8: removing plate

9: base sheet supply roll 10: container

11: Re-peelable adhesive sheet 12: Re-peelable adhesive sheet winding roll

13: Base sheet surface 14: Adhesive layer forming surface

15: Band-shaped adhesive layer 16: Re-peelable adhesive sheet laminate

In the re-peelable pressure-sensitive adhesive sheet of the present invention, various base sheets may be used as the base sheet, but may be appropriately selected depending on the purpose of use. As a specific example of a base sheet, For example, Paper, Synthetic paper, such as quality paper, art paper, a coated paper, a graft paper, laminated paper which laminated thermoplastic resin, such as polyethylene resin, on these paper base materials; Metal foils such as aluminum foil, copper foil and iron foil; Porous material sheets such as nonwoven fabrics; Furthermore, polyolefin resin, such as polyethylene resin, polypropylene resin, various olefin copolymer resins, polyethylene terephthalate resin, polybutylene terephthalate resin, polyester resins, such as polyethylene naphthalate resin, polystyrene resin, polyvinyl chloride resin, acrylic The plastic sheet which consists of resin, a polycarbonate resin, a polyamide resin, a fluororesin, and the mixture of 2 or more types of these resins, or 2 or more types of laminated bodies of these sheets, etc. are mentioned.

In order to provide printability, these plastic sheets may be sheets in which ink repair layers corresponding to various printing methods are formed on the surface opposite to the adhesive layer. Moreover, when a plastic sheet is transparent, a letter and a pattern may be printed on the surface which forms the adhesion layer of a plastic sheet.

Moreover, the surface which forms the adhesion layer of these plastic sheets can be surface-treated by methods, such as an oxidation method and an uneven | corrugated method, as needed in order to improve adhesiveness with an adhesion layer. Examples of the oxidation method include corona discharge surface treatment, chromic acid surface treatment (wet), flame surface treatment, hot air surface treatment, ozone and ultraviolet irradiation surface treatment, and the like. Moreover, as said uneven | corrugated method, a sandblasting method, a solvent treatment method, etc. are mentioned, for example. Although these surface treatment methods are suitably selected according to the kind of base material sheet, generally, the corona discharge surface treatment method is used preferably from a point of an effect and operability. In addition, primer treatment may be performed.

In addition, when using a paper material and a nonwoven fabric as a base material sheet, a gap filling layer can be formed between a base material sheet and an adhesion layer as needed. As the gap filling layer, usually, one or more kinds of styrene-butadiene copolymer, acrylic resin, polyester resin, polyurethane resin, polystyrene resin, etc. are main components, and clay, silica, calcium carbonate, titanium oxide, The layer which consists of what added fillers, such as zinc oxide, etc. is mentioned. The coating amount of the gap filling layer is not particularly limited, but is preferably in the range of 0.1 to 300 g / m 2.

On the other hand, although it is not necessary to perform a peeling process to the opposite side of the surface which forms the adhesion layer of a base material sheet, it is preferable to perform the peeling process preferably. It is preferable that a peeling process forms a peelable layer in the single side | surface of a base sheet by apply | coating, printing, or transferring a peeling agent. Although various things can be mentioned as a peeling agent to be used, For example, a silicone type peeling agent, a fluorine type peeling agent, an olefin type peeling agent, an alkyd type peeling agent, etc. are mentioned. As application amount of a peelable layer, 0.1-10.0 g / m <2> is preferable and 0.5-4 g / m <2> is especially preferable.

In this invention, the adhesion layer is formed in the single side | surface of the said base sheet (when surface treatment is performed in order to improve the adhesiveness of a base material sheet and an adhesion layer on the surface of a base material sheet).

The pressure-sensitive adhesive layer is an adhesive containing a spherical pressure-sensitive adhesive and an emulsion-type binder pressure-sensitive adhesive, wherein the spherical pressure-sensitive adhesive polymerizes an ethylenically unsaturated monomer in the presence of 0.1 to 3 parts by weight of polyacrylic acid with respect to 100 parts by weight of an ethylenically unsaturated monomer component. In spherical pressure-sensitive adhesive (B) obtained by adding 0.1 to 7 parts by weight of polyacrylic acid with respect to 100 parts by weight of the solid content of the spherical pressure-sensitive adhesive to the spherical pressure-sensitive adhesive (A) obtained by polymerizing or an ethylenically unsaturated monomer. Consists of.

As a spherical adhesive of said (A) or (B), the spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer is preferable, and the acryl-type spherical adhesive containing especially a (meth) acrylate monomer is preferable.

An acryl-type spherical adhesive is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethyl (meth), for example. (Meth) acrylate monomers such as) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxy (meth) acrylate, N-methylol (meth) acrylate, glycidyl (meth) acrylate It can be obtained by copolymerizing at least 1 sort (s) selected from these as a main component, and if necessary, copolymerizing this and monomers, such as (meth) acrylic acid, maleic acid, vinyl acetate, vinyl propionate, styrene, and acrylonitrile, as needed. have.

As a specific manufacturing method of an acryl-type spherical adhesive, the method of manufacturing the water suspension of a spherical adhesive is mentioned by various methods, such as a suspension polymerization method and the method of suspending in water after solution polymerization. Thereby, a spherical adhesive can be obtained.

The average particle diameter of the particles of the spherical pressure-sensitive adhesive is not particularly limited, but is preferably in the range of 20 to 150 µm, particularly preferably in the range of 30 to 80 µm. If the average particle diameter of the particle | grains of a spherical adhesive is less than 20 micrometers, the characteristic as a spherical adhesive may hardly be exhibited, adhesive force may become strong too much and re-peelability may fall. On the contrary, when the average particle diameter of the particle | grains of a spherical adhesive exceeds 150 micrometers, since the adhesive area with a to-be-adhered body becomes small, there exists a possibility that it becomes difficult to obtain favorable adhesive force.

The spherical pressure-sensitive adhesive of (A) uses polyacrylic acid as a suspension stabilizer in the polymerization of ethylenically unsaturated monomers, and maintains the stability of the polymerization reaction of the ethylenically unsaturated monomers well and removes them at the time of partial coating. In terms of maintaining satisfactorily, the amount of polyacrylic acid used is 0.1 to 3 parts by mass, and more preferably 0.5 to 2.8 parts by mass based on 100 parts by mass of the ethylenically unsaturated monomer component.

As a suspension stabilizer, you may use another suspension stabilizer together with polyacrylic acid as needed.

As another suspension stabilizer, For example, water-soluble polymers, such as gelatin, starch, casein, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, polyacrylamide; Sodium alkylbenzenesulfonate, sodium alkyldiphenyletherdisulfonate, sodium lauryl sulfate, sodium polyoxyethylenealkylether sulfate, sodium alkylnaphthalenesulfonate, sodium fatty acid, sodium dodecylbenzenesulfonate, sodium alkylenedisulfonate, die Sodium alkyl sulfosuccinate, sodium monoalkyl sulfosuccinate, sodium sodium polyoxyethylene alkyl ether sulfate, sodium sodium polyoxyethylene alkyl ether phosphoric acid, sodium sodium polyoxyalkylene alkyl ether, sodium lignin sulfonate, melamine resin sulfonic acid Anionic surfactant, polyoxyethylene octylphenyl ether, polyoxyethylene nonyl phenol ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan Fatty acid ester, polyoxyethylene sorbitol fatty acid ester And one or more kinds of nonionic surfactants such as glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and poly (oxyethylene / oxypropylene) block copolymers. Among these, methylcellulose and polyacrylamide are particularly preferable in combination with polyacrylic acid. It is preferable that the total used amount of a suspension stabilizer is 0.1-15 mass parts with respect to 100 mass parts of ethylenically unsaturated monomer components. If it is less than 0.1 mass part with respect to 100 mass parts of ethylenically unsaturated monomer components, a removal property will deteriorate, and if it exceeds 15 mass parts, moisture resistance may fall.

The spherical pressure-sensitive adhesive of (B) is a spherical pressure-sensitive adhesive obtained by adding polyacrylic acid to a spherical pressure-sensitive adhesive obtained by polymerizing an ethylenically unsaturated monomer in the absence of polyacrylic acid, and the polyacrylic acid is spherical with an emulsion-type binder pressure-sensitive adhesive. Since it is added as a dispersing agent of an adhesive, the usage-amount of polyacrylic acid is 0.1-7 mass parts with respect to 100 mass parts of solid content of a spherical adhesive from the point which maintains the removability at the time of partial coating favorable, Preferably it is 1- 5 parts by mass.

Moreover, when superposing | polymerizing an ethylenically unsaturated monomer in the absence of polyacrylic acid, you may use the said suspension stabilizer other than polyacrylic acid as a suspension stabilizer, and a preferable thing is also the same.

As a dispersing agent, you may use another dispersing agent together with polyacrylic acid as needed.

As other dispersing agents, if desired, for example, water-soluble polymers such as gelatin, starch, casein, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, polyacrylamide, or anionic interfaces already listed above. At least 1 type, such as an active agent and a nonionic surfactant, is mentioned preferably. It is preferable that the total used amount of a dispersing agent is 0.1-10 mass parts with respect to 100 mass parts of solid content of a spherical adhesive. If it is less than 0.1 mass part with respect to 100 mass parts of solid content of a spherical adhesive, a removeability will be bad, and when it exceeds 10 mass parts, moisture resistance will run short and the problem of physical property deterioration may arise.

In the adhesive of this invention, only any one of said spherical adhesive of said (A) or (B) may be used, and may mix and use both.

Moreover, when using a suspension stabilizer or a dispersing agent, it is preferable to add, after melt | dissolving a suspension stabilizer or dispersing agent in an appropriate amount of water.

Here, the polyacrylic acid used as the spherical pressure-sensitive adhesive of (A) or (B) may be a homopolymer of acrylic acid, or a copolymer obtained by copolymerizing other polymerizable monomers other than acrylic acid within the range of not impairing the object of the present invention. It may be sufficient as it, and the modified polyacrylic acid reacted with the modifier may be sufficient. 3000-20000 are preferable and, as for the weight average molecular weight of polyacrylic acid, 5000-15000 are especially preferable.

It is preferable that the coagulation | solidification rate by a marron test of the adhesive which comprises an adhesion layer is 5.0 mass% or less. When the coagulation rate by maron test exceeds 5.0 mass%, the application | coating stability of an adhesive may be inferior. The coagulation rate by the maron test is more preferably 4.0% by mass or less, and particularly preferably 3.0% by mass or less. In addition, the measurement of the coagulation rate by a marron test is performed based on JISK6387-1982 or JISK6392-1982.

The emulsion-type binder pressure-sensitive adhesive used in the present invention can be used a variety of emulsion-type binder pressure-sensitive adhesive without particular limitation. Especially, an acrylic emulsion type binder adhesive is preferable from a viewpoint of performance, such as adhesive characteristic, weather resistance, and heat resistance.

An acrylic emulsion type binder adhesive contains acrylic acid resin as a main component. As for this acrylic acid resin, the (meth) acrylic acid ester system monomer and (meth) acrylic acid ester resin obtained by superposing | polymerizing another ethylenically unsaturated monomer as needed are preferable. Examples of the (meth) acrylic acid ester monomer and other ethylenically unsaturated monomers include those similar to those described above as raw materials for the acrylic spherical pressure sensitive adhesive.

Moreover, it is preferable that acrylic acid type resin is bridge | crosslinking suitably with an internal crosslinking agent and / or an external crosslinking agent.

In addition, an internal crosslinking agent refers to the crosslinking-type reactive monomer which can introduce | transduce a crosslinking structure in a polymer molecule at the time of superposition | polymerization here, and an external crosslinking agent can crosslink by reacting the crosslinkable functional group which exists in the molecule | numerator of the polymerized polymer. Point out.

As an internal crosslinking agent, a keto group containing ethylenically unsaturated monomer, an aldo group containing ethylenically unsaturated monomer, etc. are mentioned preferably. As a keto group containing ethylenically unsaturated monomer, acrolein, diacetone acrylamide, formyl styrol, vinyl alkyl ketone, diacetone (meth) acrylate, (meth) acryloxyalkyl acrylate, etc. are mentioned, for example. An internal crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. The internal crosslinking agent is blended during the polymerization of the acrylic acid resin to crosslink it. As for the compounding quantity of an internal crosslinking agent, 0-5 mass parts is preferable with respect to 100 mass parts of acrylic resins.

Examples of the external crosslinking agent include isocyanate compounds, epoxy compounds, melamine compounds, aziridine (ethyleneimine) compounds, hydrazide compounds, oxazoline compounds, carbodiimide compounds, and urea compounds. And dialdehyde compounds, metal chelate compounds, metal alkoxide compounds, metal salts and the like. An external crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. The external crosslinking agent is blended with the acrylic acid resin obtained by polymerization to crosslink it. As for the compounding quantity of an external crosslinking agent, 0-5 mass parts is preferable with respect to 100 mass parts of acrylic resins.

In the acrylic emulsion binder adhesive, any one of an internal crosslinking agent and an external crosslinking agent may be used, or both.

Since an acrylic emulsion type binder adhesive is an emulsion, the particle | grains of an acrylic resin are disperse | distributing in the aqueous medium, The solid content is 15-75 mass% is preferable.

As a manufacturing method of an acrylic emulsion binder adhesive, various methods can be used without a restriction | limiting in particular. As a specific example of the manufacturing method of an acrylic emulsion type binder adhesive, For example, the (meth) acrylic acid ester monomer which is a raw material of acrylic acid resin, and other ethylenically unsaturated monomer as needed are added to the aqueous medium containing an emulsifier first. And emulsification treatment, and polymerization is carried out in the presence of a polymerization initiator. It is preferable to perform an emulsification process using a high pressure homogenizer or an ultrasonic wave. Moreover, as a polymerization initiator, various polymerization initiators used in emulsion radical polymerization, for example, an organic peroxide, an azo compound, a persulfate, various redox catalysts, etc. are mentioned. Although polymerization can be performed at various temperature, 30-100 degreeC is preferable and 40-90 degreeC is more preferable.

The content ratio of the spherical pressure-sensitive adhesive and the emulsion-type binder pressure-sensitive adhesive in the pressure-sensitive adhesive used in the present invention is preferably in the range of 100: 5 to 100: 50 in terms of solid content mass ratio, and the range of 100: 10 to 100: 35 Particularly preferred. When the content rate of a spherical adhesive is less than the said range, there exists a possibility that the repeelability of the repeelable adhesive sheet obtained may become inadequate. On the other hand, when the content rate of a spherical adhesive is more than the said range, the adhesive force with respect to a to-be-adhered body may fall.

An adhesive can contain one or more of the various additives normally used for an adhesive as needed, within the range which does not impair the objective of this invention. As various additives, a tackifier, a plasticizer, a filler, an antioxidant, a ultraviolet absorber, a preservative, an antifungal agent, a dye, a pigment, a fragrance | flavor, etc. are mentioned, for example.

In the present invention, the coating method of the pressure-sensitive adhesive can be applied to various coating methods, for example, roll coating method, roll reverse coating method, knife coating method, roll knife coating method, roll knife reverse coating method, bar coating method Etc. can be mentioned.

Although the thickness of an adhesion layer does not have a restriction | limiting in particular, Usually, what is necessary is just 0.5-5 g / m <2> in the mass after drying, Preferably it is 1-3 g / m <2>.

It is preferable that the adhesive force with respect to the stainless steel plate of an adhesion layer is 1.0N / 105mm or more normally, It is more preferable that it is 1.5N / 105mm or more, It is especially preferable that it is 2.0N / 105mm or more. Although the upper limit of the adhesive force with respect to the stainless steel plate of an adhesion layer does not have a restriction | limiting in particular, Usually, 4.0 N / 105 mm or less is preferable.

Moreover, the ratio of the adhesive force with respect to a stainless steel plate, and the adhesive force with respect to the base material sheet surface (if the peeling process is performed in order to improve the peelability of a base material sheet and an adhesion layer on the surface of a base material sheet) 1 It is preferable that it is the range of 1: 0.2-1: 1, It is more preferable that it is the range of 1: 0.2-1: 0.8, It is especially preferable that it is the range of 1: 0.2-1: 0.6.

Next, the manufacturing method by the roll reverse coat method of the repeeling adhesive sheet of this invention is demonstrated based on drawing.

In FIG. 1, the pressure-sensitive adhesive layer transfer metal roll 3 and the pressure-sensitive adhesive layer pressure roll 7 rotate in the same direction, and the pressure-sensitive adhesive 2 stored in the container 10 is transferred to the pressure-sensitive adhesive layer transfer metal roll 3. It is apply | coated to the surface of the adhesive layer 4 of constant thickness is formed. In addition, the surface of the pressure-sensitive adhesive layer pressing roll 7 is prevented from adhering the pressure-sensitive adhesive by the removal plate 8 of the pressure-sensitive adhesive. Next, the adhesive layer 4 is partially removed by the blade 6 to form a band-shaped adhesive layer 5, and the band-shaped adhesive layer 5 is formed on the surface of the base sheet supply roll 9. It is transferred to one side of the wound base sheet 1. Thereby, the re-peelable adhesive sheet 11 in which the adhesion layer is formed in one surface of the base sheet is manufactured.

Although the width | variety of a strip | belt-shaped adhesive layer should just select suitably according to the use of a re peelable adhesive sheet, it is preferable to make it the area of a strip | belt-shaped adhesive layer become 3 to 90% of the area of a re peelable adhesive sheet, and 5 to It is more preferable to make it 60%. Moreover, what is necessary is just to set it as about 5 to 35% of the area of each re-peelable adhesive sheet laminated | stacked, when setting it as an adhesive memo sheet laminated body.

Moreover, the number of blades may be made into 2 or more sheets, and the number of strip | belt-shaped adhesive layers may be made into 2 or 3 or more pieces. It is also possible to form a plurality of band-shaped pressure-sensitive adhesive layers so that at least one groove is formed in one blade and the pressure-sensitive adhesive layer is not removed from the groove portion.

In addition, when forming an adhesive layer in one whole surface of a base material sheet, without attaching the blade 6, without removing the adhesive layer 4 apply | coated to the surface of the adhesive layer transfer metal roll 3, By transferring this adhesive layer to the single side | surface of a base sheet, the re peelable adhesive sheet in which the adhesive layer was formed in one whole surface can be manufactured.

Examples of the blade 6 include various materials, and a polyester resin such as polyethylene terephthalate resin is preferable.

As shown in FIG. 2 (left figure), the re-peelable adhesive sheet of this invention may be made into the shape of the re-peelable adhesive sheet odor roll 12 of the state wound up in roll shape. The re-peelable pressure-sensitive adhesive sheet 11 has a base sheet surface 13 facing outward, and the re-peelable pressure-sensitive adhesive sheet 11 is wound with the pressure-sensitive adhesive layer forming surface 14 inward. Two strip | belt-shaped adhesive layers 15 are formed in the adhesion layer formation surface 14 of this re-peelable adhesive sheet 11.

In addition, in the re-peelable adhesive sheet of the present invention, as shown in FIG. 2 (right figure), a plurality of sheets of the re-peelable adhesive sheet 11 are adjacent to the surface of the base sheet. It is good also as a shape of the re-peelable adhesive sheet laminated body 16 laminated | stacked by making the adhesion layer of () contact. In addition, in FIG. 2 (right figure), the laminated peelable adhesive sheet laminated body 16 is cut | disconnected along a dotted line, and it can be set as the re peelable adhesive sheet laminated body of a suitable size. At this time, it is preferable at the time of cutting | disconnection to add a pressure to a pressure port in the vicinity of a cutting | disconnection part, so that the position of a cut | disconnection part may not shift. The re-peelable pressure-sensitive adhesive sheet of the present invention has a feature that there is little variation in adhesive force and peeling force due to the light weight.

The re-peelable adhesive sheet of this invention has the uniform adhesive force with little unevenness of adhesive force by the weight of pressure, and can stick and peel. In addition, the method of manufacturing the re-peelable pressure-sensitive adhesive sheet of the present invention is not only excellent in removability when the pressure-sensitive adhesive is removed by a blade during partial coating, but also good in separation of the pressure-sensitive adhesive layer, and the width of the band-shaped pressure-sensitive adhesive layer is improved. It can produce as set, and hardly agglomerates generate | occur | produce in an adhesive, and at the same time, a bubble is hardly generated. In addition, the re-peelable pressure-sensitive adhesive sheet laminate of the present invention has the characteristics of the re-peelable pressure-sensitive adhesive sheet, has little unevenness of peeling force due to the weight of pressure, and has uniform and soft peelability, and re-peeling. After peeling off the adhesive sheet from the laminate, it can be hardly curled.

The re-peelable adhesive sheet of this invention can be used as a laminated body, and can stick to various other to-be-adhered bodies.

Next, an Example demonstrates this invention further more concretely. In addition, this invention is not restrict | limited at all by these examples.

Next, an Example demonstrates this invention concretely. However, this invention is not limited at all by these examples.

The test method of the re peelable adhesive sheet obtained by the Example and the comparative example is described below.

(1) Adhesion Test of Re-peelable Adhesive Sheet

The repeelable adhesive sheet was affixed on the stainless steel plate which is a to-be-adhered body, and the adhesive force after 30 minutes was measured according to JISZ0237. The unit is N / 105 mm.

(2) Peel force measurement test of re-peelable adhesive sheet

Take two sheets with the re-peelable adhesive sheet laminated, and fix the surface on which the pressure-sensitive adhesive layer of one re-peelable adhesive sheet is formed with a double-sided tape to a stainless steel plate, and use the re-peelable adhesive sheet with a tensile tester. Then, the peeling force (adhesive force) when peeling rate 300 mm / min and peeling angle 180 degree was measured. The unit is N / 105 mm.

(3) non-uniformity of adhesion and peeling force

After leaving the re-peelable pressure-sensitive adhesive sheet winding roll for 1 week, the adhesive force and peeling force of the re-peelable pressure-sensitive adhesive sheet of the surface portion of the re-peelable pressure-sensitive adhesive sheet winding roll were measured by the methods of (1) and (2). In addition, the adhesive force and peeling force of the re-peelable adhesive sheet in the vicinity of the core portion of the re-peelable pressure-sensitive adhesive sheet winding roll were measured, and the two were compared, and the difference between them was not 20% or less based on the adhesive force and the peeling force of the core portion. It was said that this "none", and evaluated that the difference of both was more than 20% based on the adhesive force of the core part, and peeling force as "it exists."

(5) Coagulation rate measurement test by Maron test

In accordance with JIS K6387-1982, the container containing the sample for measurement is pressed by rotating the disc at a constant pressure, rotated at a constant speed, and the coagulated product is filtered through a 200 mesh metal mesh to form an emulsion. After collection, the resultant was dried at 105 ° C. for 1 hour, and allowed to stand in a desiccator for 30 minutes and then weighed. The solidification rate was computed from the mass and the mass of the sample before a measurement. The pressing force was 15 kgf, the sample temperature was 25 ° C., the sample mass was 50 g, the rotation speed was 1000 rpm, and the rotation time was 10 minutes.

(6) removability test

Rotate the metal roll having an outer diameter of 59 mm to which the adhesive coating liquid is attached at 100 rpm, and press-contact the polyethylene terephthalate resin blade to it to remove the coating liquid of the adhesive from the blade portion in pressure contact, and A band-shaped adhesive layer was formed on the surface of the metal roll. The degree to which the pressure-sensitive adhesive of the band-shaped pressure-sensitive adhesive layer protruded to the surface of the metal roll from which the coating liquid of the pressure-sensitive adhesive was removed was visually observed and evaluated according to the following criteria.

○: adhesive does not come out

(Triangle | delta): The adhesive sticks out slightly

×: pressure-sensitive adhesive is prominent

(7) Penetration test of adhesive

In the roll processing, one adhesive memo sheet laminate produced by the blade removal method is peeled off, and affixed to the back side of kraft paper (Fuji Shiko Co., Ltd., product name "ate board") to promote penetration for 168 hours under a forced drying environment of 70 ° C. I was. Then, after leaving for 24 hours in a standard environment, the adhesive memo sheet was peeled off, the state of penetration was visually observed and evaluated according to the following criteria.

○: no penetration

△: slight penetration

×: penetration

(8) Curling property after peeling of a peelable adhesive sheet

One adhesive memo sheet laminated body was peeled off, the extent to which the adhesive memo sheet was curled was visually observed, and it evaluated according to the following criteria.

○: not curled

×: curled

Example 1

(1) Preparation of Spherical Adhesive

100 parts by mass of mixed monomer mixed with 98 parts by mass of 2-ethylhexyl acrylate and 2 parts by mass of acrylic acid, 4 parts by mass of methyl cellulose as a suspension stabilizer, 2 parts by mass of polyacrylic acid (weight average molecular weight 10000), and polyoxyethylene nonylphenol 4 mass parts of ether is added to 260 mass parts of ion-exchange water, 1 mass part of polymerization initiators (benzoyl peroxide) are added, and suspension polymerization is performed at 80 degreeC for 5 hours, and 50 micrometers of average particle diameters and 30 mass% of solid content concentration Acrylic suspension type spherical adhesive (A) was manufactured.

(2) Preparation of adhesive

With respect to 100 mass parts of solid content of the spherical adhesive obtained by said (1), 50 mass parts of acrylic emulsion type binder adhesives (The Toyo Ink Corporation company make, brand name "Olivine BPW5320", solid content 58.5 mass%), and a dispersant are car A pressure-sensitive adhesive was prepared by mixing a liquid obtained by dissolving 2 parts by mass of methyl methyl cellulose in 65 parts by mass of ion-exchanged water and 6 parts by mass of a rosin-based tackifier having a softening point of 150 ° C.

(3) Preparation of laminated body of re-peelable adhesive sheet

By the method shown in FIG. 1, the laminated body of the removable adhesive sheet was created. Specifically, the pressure-sensitive adhesive is applied onto the surface of the application roll which is the pressure-sensitive adhesive layer transfer metal roll 3 to form a pressure-sensitive adhesive layer 4, and then partially by the polyester resin blade 6. Base material sheet (manufactured by Lintec Co., Ltd., product name), wherein the pressure-sensitive adhesive layer 4 is removed to form a band-shaped pressure-sensitive adhesive layer 5, and the band-shaped pressure-sensitive adhesive layer 5 is wound on the surface of the base sheet supply roll 9 FIT MATE Yohakuri City Lemon 72G ”, sheet weight: 72 g / m 2, release agent: long-chain alkyl-based release agent, application amount of release agent: 1.5 g / m 2) on non-peeled surface The re-peelable adhesive sheet 11 in which the adhesive layer is formed on a part of the surface of the base sheet is transferred, is wound in a roll shape by one layer winding, and the re-peelable adhesive sheet winding roll 12 (winding water 300 stories). The coating amount after drying of the adhesion layer was 7 g / m <2>. The single-layered roll-shaped adhesive sheet was cut out, a plurality of re-peelable pressure-sensitive adhesive sheets were prepared, each of the pressure-sensitive adhesive layers 15 and the base sheet surface 13 were laminated to face each other, and the re-peelable pressure-sensitive adhesive sheet The laminated body 16 was created, it cut | disconnected by the dotted line shown in FIG. 2 (right figure), and the adhesive memo sheet laminated body was created. The performance of this adhesive sheet is shown in Table 1.

Example 2

Except having made the addition amount at the time of superposition | polymerization of polyacrylic acid into 2.8 mass parts with respect to 100 mass parts of mixed monomers, the weight average molecular weight of this polyacrylic acid is 7000, and the average particle diameter of the spherical adhesive obtained is 35 micrometers. In the same manner as in 1, an adhesive memo sheet laminate was prepared. The performance of this adhesive sheet is shown in Table 1.

Example 3

In Example 1 (1), the acrylic suspension type spherical adhesive (B) of 50 micrometers of average particle diameters is manufactured using 100 mass parts of mixed monomers, and 4 mass parts of methylcellulose and 2 mass parts of polyacrylamides as a suspension stabilizer. (The difference from Example 1 was that polyacrylic acid was not added at the time of suspension polymerization, but polyacrylamide was added instead), and 5 mass parts of carboxymethyl cellulose and polyacrylic acid (weight average as a dispersant at the time of adhesive preparation) A pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that 2 parts by mass of molecular weight were added, and a re-peelable pressure-sensitive adhesive sheet and a re-peelable pressure-sensitive adhesive sheet laminate were prepared. The performance of this adhesive sheet is shown in Table 1.

Example 4

An adhesive memo sheet laminate was prepared in the same manner as in Example 3 except that the amount of polyacrylic acid added was 1 part by mass based on 100 parts by mass of the solid content of the spherical adhesive, and the weight average molecular weight of the polyacrylic acid was 7000. The performance of this adhesive sheet is shown in Table 1.

Comparative Example 1

In Example 1 (1), 100 mass parts of mixed monomers, 4 mass parts of polyacrylamides, and 2 mass parts of methylcellulose are used as a suspension stabilizer, and it is the same as that of Example 1, and the re-peelable adhesive sheet and The re-peelable pressure-sensitive adhesive sheet laminate was prepared. The performance of this adhesive sheet is shown in Table 2.

Comparative Example 2

In Example 1 (1), 4 mass parts of methylcellulose and 2 mass parts of polyvinyl alcohol are used as 100 mass parts of mixed monomers and a suspension stabilizer, and it is the same as that of Example 1, and the re-peelable adhesive sheet and The re-peelable pressure-sensitive adhesive sheet laminate was prepared. The performance of this adhesive sheet is shown in Table 2.

Example 1 Example 2 Example 3 Example 4

Of spherical adhesive
Raw material
Furtherance 2-ethylhexyl acrylate 98 98 98 98 Acrylic acid 2 2 2 2 Methyl cellulose 4 4 4 4 Polyacrylic acid 2 2.8 - - Polyacrylamide - - 2 2 Polyvinyl alcohol - - - - Benzoyl peroxide One One One One Polyoxyethylene nonyl phenol ether 4 4 4 4 Ion-exchange water 260 260 260 260 Average particle size of the spherical pressure-sensitive adhesive (㎛) 50 35 50 50

Adhesive
Furtherance

Spherical glue
(30 mass% of solids) 333.3 333.3 333.3 333.3 BPW5320
(58.5 mass% of solid content) 50 50 50 50 Rosin Type Tackifier 6 6 6 6 Carboxymethylcellulose 2 2 - - Polyacrylic acid - - 2 One Ion-exchange water 65 65 65 65

evaluation

Coagulation rate of Maron test 2.8 0.89 0.4 1.05 Removability ○ ○ ○ ○ Adhesive force (N / 105㎜) 2.73 2.05 2.20 2.30 Peeling force (N / 105 mm) 0.76 1.10 0.58 0.93 Ratio of adhesive force and peeling force 0.28 0.53 0.26 0.40 Adhesion (Surface Part) 2.73 2.05 2.20 2.30 Adhesion (deep in roll) 2.52 1.95 2.05 2.10 Peel force (surface portion of roll) 0.76 1.10 0.58 0.93 Peel force (deep of roll) 0.85 1.05 0.70 1.03 Nonuniformity of Adhesion and Peeling Force none none none none Penetration of Adhesive ○ ○ ○ ○ Curling property ○ ○ ○ ○

Comparative Example 1 Comparative Example 2

Spherical shape
Adhesive
Raw material composition

2-ethylhexyl acrylate 98 98 Acrylic acid 2 2 Methyl cellulose 2 4 Polyacrylic acid - - Polyacrylamide 4 - Polyvinyl alcohol - 2 Benzoyl peroxide One One Polyoxyethylene nonyl phenol ether 4 4 Ion-exchange water 260 260 Average particle size of the spherical pressure-sensitive adhesive (㎛) 50 50

Adhesive
Furtherance

Spherical Adhesive (Solid 30% by Mass) 333.3 333.3 BPW5320 (58.5 mass% of solids) 50 50 Rosin Type Tackifier 6 6 Carboxymethylcellulose 2 2 Polyacrylic acid - - Ion-exchange water 65 65

evaluation

Coagulation rate of Maron test 6.6 0.4 Removability × × Adhesion (N / 105㎜) 1.55 2.41 Peeling force (N / 105 mm) 1.86 4.08 Ratio of adhesive force and peeling force 1.20 1.69 Adhesion (Surface Part) 1.55 2.41 Adhesion (deep in roll) 1.10 1.95 Peel force (surface portion of roll) 1.86 4.08 Peel force (deep of roll) 2.50 5.05 Nonuniformity of Adhesion and Peeling Force has exist has exist Penetration of Adhesive × ○ Curling property × ×

Claims

A pressure-sensitive adhesive containing a spherical pressure-sensitive adhesive and an emulsion-type binder pressure-sensitive adhesive is coated on one side of the base sheet to form a pressure-sensitive adhesive layer, and the total amount of the suspending stabilizer containing polyacrylic acid and methyl cellulose is ethylene-based. Ethylenic unsaturated in presence of polyacrylic acid and methylcellulose as suspension stabilizer which is 0.1-15 mass parts with respect to 100 mass parts of unsaturated monomer components, and the usage-amount of polyacrylic acid is 0.1-3 mass parts with respect to 100 mass parts of ethylenically unsaturated monomer components. Spherical adhesive obtained by adding 0.1-7 mass parts of polyacrylic acid with respect to 100 mass parts of solid content of a spherical adhesive to the spherical adhesive obtained by superposing | polymerizing a monomer or the spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer ( B) re-peelable pressure-sensitive adhesive sheet, characterized in that.

The re-peelable pressure-sensitive adhesive sheet according to claim 1 is wound in a roll shape, characterized in that the re-peelable pressure-sensitive adhesive sheet winding rolls.

A pressure-sensitive adhesive containing a spherical pressure-sensitive adhesive and an emulsion-type binder pressure-sensitive adhesive is partially applied to one side of the base sheet to form a pressure-sensitive adhesive layer, and the total amount of the suspension stabilizer containing the polyacrylic acid and methyl cellulose is used. 0.1-15 mass parts with respect to 100 mass parts of ethylenically unsaturated monomer components, and the use amount of polyacrylic acid is 0.1-3 mass parts with respect to 100 mass parts of ethylenically unsaturated monomer components, and in the presence of polyacrylic acid and methylcellulose as suspension stabilizer Spherical shape obtained by adding 0.1-7 mass parts of polyacrylic acid with respect to 100 mass parts of solid content of a spherical adhesive to the spherical adhesive obtained by superposing | polymerizing an unsaturated unsaturated monomer (A) or a spherical adhesive obtained by superposing | polymerizing an ethylenically unsaturated monomer. Re-peelable pressure-sensitive adhesive sheet, characterized in that the pressure-sensitive adhesive (B).

The method according to claim 1 or 3,

The adhesive is a pressure-sensitive adhesive having a coagulation rate of 5.0% by mass or less by the Maron test.

The method according to any one of claims 1, 3 or 4,

The adhesive force of the adhesive layer on the stainless steel plate is 1.0 N / 105 mm or more, and the ratio of the adhesive force on the stainless steel plate and the adhesive force on the surface of the base sheet is in the range of 1: 0.2 to 1: 1. .

A plurality of sheets of the repeelable pressure-sensitive adhesive sheet according to any one of claims 1, 3, 4 or 5 are laminated. A repeelable pressure-sensitive adhesive sheet laminate.

After applying the pressure-sensitive adhesive containing the spherical pressure-sensitive adhesive and emulsion binder pressure-sensitive adhesive on the surface of the pressure-sensitive adhesive layer transfer metal roll, the applied pressure-sensitive adhesive is partially removed by a blade to form a band-shaped pressure-sensitive adhesive layer, A method of producing a re-peelable pressure-sensitive adhesive sheet by transferring the band-shaped pressure-sensitive adhesive layer to one side of the base sheet, wherein the total amount of the suspending stabilizer containing polyacrylic acid and methyl cellulose is 100% by mass of the ethylenically unsaturated monomer component. It is 0.1-15 mass parts with respect to a part, and the polyacrylic acid is obtained by superposing | polymerizing an ethylenically unsaturated monomer in presence of polyacrylic acid and methylcellulose as a suspension stabilizer which is 0.1-3 mass parts with respect to 100 mass parts of ethylenically unsaturated monomer components. Spherical pressure-sensitive adhesive (A) or spherical pressure-sensitive adhesive obtained by polymerizing an ethylenically unsaturated monomer 0.1 to the releasable method of producing a pressure-sensitive adhesive sheet, characterized in that 7 parts by mass of polyester adhesive (B) obtained by adding the spherical portion with respect to solid content of acrylic acid 100 parts by mass of the spherical pressure-sensitive adhesive portion.