JP2006076251A - Adhesive sheet for removing solvent-containing substance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a sheet for removing a solvent-containing substance by which the solvent-containing substance such as paste turning around to the back side of a screen printing plate can be efficiently removed while further preventing the occurrence of static electricity. <P>SOLUTION: The adhesive sheet for removing a solvent-containing substance has a constitution in which an adhesive layer is formed to at least one face of a base material via an antistatically processed layer. The antistatically processed layer is formed of an antistatic agent containing a conductive polymer in which an acrylic monomer having a group containing a quaternary ammonium salt is at least made as a monomer component. It is preferable that the thickness of the antistatically processed layer is 0.01-5 μm. It is also preferable that the adhesive layer is formed of an adhesive composition containing (A) an acrylic polymer containing a carboxy group, (B) an amine-based compound containing a plurality of hydroxy groups, and (C) a polyisocyanate compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention includes, for example, a paste (ink) that is turned on the back side of a screen printing plate during screen printing, ink that is attached to rolls of a printing machine such as offset printing, gravure printing, flexographic printing, and the like, and an ink jet printer The present invention relates to a cleaning adhesive sheet for removing solvent-containing materials such as ink and paint.

  Solvent-containing materials such as semi-solid materials containing solvents such as paste and ink are widely used in the fields of printing, paints, adhesives and the like. However, when such a solvent-containing material is excessively present at a predetermined site or is present at an unnecessary site, it can contaminate machines, equipment, hands, etc. Problems are likely to occur. For example, in screen printing, after a certain number of times of printing, paste (ink) on the screen printing plate turns back to contaminate the printed material, or bleeding occurs in the printed image, making accurate and beautiful printing impossible. It becomes a state.

  Conventionally, in order to prevent such bleeding at the time of screen printing, a method is known in which the paste on the back side of the plate is removed using an adhesive sheet. For example, an adhesive sheet for cleaning a screen printing plate having a high cleaning effect has been proposed that can reliably remove the paste on the back side of the screen printing plate without removing the emulsifier of the screen printing plate. Patent Document 1).

Japanese Patent No. 3281323

  However, generation of static electricity has been a problem when solvent-containing materials such as paste are removed using a pressure-sensitive adhesive sheet-removing pressure-sensitive adhesive sheet such as a screen printing plate cleaning pressure-sensitive adhesive sheet. When static electricity occurs, when the adhesive sheets approach each other on the pass line, the adhesive sheets may be attracted or repelled due to the influence of static electricity. Further, when the pressure-sensitive adhesive sheet is brought close to the screen printing plate to which the paste (ink) is adhered, the paste (ink) may be scattered due to the influence of static electricity. Furthermore, when an operator touches the pressure-sensitive adhesive sheet during work, there may be a feeling of discomfort due to a shock of static electricity. In addition, dust and dust around the surface adhere to the adhesive sheet due to the influence of static electricity, which may cause a problem in paste (ink) removability.

  As a solution to this problem, static eliminators have been installed in the cleaning units of screen printers. However, in order to suppress the generation of static electricity in all parts, several static eliminators are installed. As a result, there was a problem that the cost disadvantage was large. In addition, if the type of the adhesive sheet or the like for removing the paste or the like is changed, the site where static electricity is generated changes, and in some cases, an additional static eliminator must be installed later.

  Therefore, by using a solvent-containing material removal sheet that has been subjected to an antistatic treatment as a solvent-containing material removal pressure-sensitive adhesive sheet such as a screen printing plate cleaning pressure-sensitive adhesive sheet, while suppressing or preventing the generation of static electricity, the paste A method for removing solvent-containing materials such as paste has been proposed, but a solvent-containing material-removing sheet capable of efficiently removing solvent-containing materials such as paste while further suppressing or preventing the generation of static electricity Is required.

  Accordingly, an object of the present invention is to remove a solvent-containing material that can be efficiently removed while further suppressing or preventing the generation of static electricity, such as a paste that is placed on the back side of the screen printing plate. To provide a sheet.

  As a result of intensive studies to achieve the above object, the present inventor has found that when an antistatic treatment layer formed of a specific conductive polymer is provided between the base material and the pressure-sensitive adhesive layer, the solvent-containing material-removing pressure-sensitive adhesive layer is removed. It has been found that the sheet can effectively suppress or prevent the generation of static electricity while maintaining excellent cleaning performance. The present invention has been completed based on these findings.

  That is, the present invention is a pressure-sensitive adhesive sheet for removing a solvent-containing material having a structure in which an adhesive layer is formed on at least one surface of a substrate via an antistatic treatment layer, and the antistatic treatment layer is A pressure-sensitive adhesive sheet for removing a solvent-containing material, characterized in that it is formed of an antistatic treatment agent containing a conductive polymer having at least a monomer component of an acrylic monomer having a group containing a quaternary ammonium salt. I will provide a.

  The thickness of the antistatic treatment layer is preferably 0.01 to 5 μm.

  The pressure-sensitive adhesive layer is formed of (A) a carboxyl group-containing acrylic polymer, (B) an amine compound containing a plurality of hydroxyl groups, and (C) a pressure-sensitive adhesive composition containing a polyisocyanate compound. It is preferable that

  The adhesive sheet for removing a solvent-containing material of the present invention can be suitably used as an adhesive sheet for cleaning a screen printing plate.

  According to the adhesive sheet for removing a solvent-containing material of the present invention, since it has the above-described configuration, the solvent-containing material such as a paste on the back side of the screen printing plate is further suppressed or prevented from generating static electricity. It can be removed efficiently. Therefore, it is not necessary to install a static electricity removal stand in a cleaning unit of a screen printing machine. Moreover, the occurrence of problems due to static electricity is eliminated, and the yield and the operation rate of equipment can be improved.

［式（１）において、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は２価の有機基を示す。また、Ｒ^3a〜Ｒ^3cは、それぞれ、同一又は異なって、水素原子又は炭化水素基を示す。さらにまた、Ｘ^-はハロゲン原子イオン、Ｒ⁴ＯＳＯ₃ ^-（Ｒ⁴は炭化水素基）、またはＲ⁵ＳＯ₃ ^-（Ｒ⁵は炭化水素基）、ＯＨ^-、ＨＣＯ₃ ^-、ＣＯ₃ ^2-、ＳＯ₄ ^2-、Ｒ⁶ＣＯＯ^-（Ｒ⁶は炭化水素基）を示し、Ｙはオキシ基又はイミノ基を示す。］ [Antistatic treatment layer]
The pressure-sensitive adhesive sheet for removing a solvent-containing material of the present invention has a structure in which a pressure-sensitive adhesive layer is formed on at least one surface of a substrate via an antistatic treatment layer, and the antistatic treatment layer comprises: Antistatic treatment containing a conductive polymer having at least a monomer component of an acrylic monomer having a group containing a quaternary ammonium salt (sometimes referred to as “quaternary ammonium salt-containing acrylic monomer”) It is formed by the agent. In such a conductive polymer in the antistatic treatment agent, the quaternary ammonium salt-containing acrylic monomer as a monomer component is a group containing at least one quaternary ammonium salt in the molecule (“first quaternary ammonium salt”). Any acrylic monomer having a quaternary ammonium salt-containing group) may be used. Specifically, an acrylic monomer represented by the following formula (1) can be suitably used as the quaternary ammonium salt-containing acrylic monomer.

[In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent organic group. R ^{3a to} R ^3c are the same or different and each represents a hydrogen atom or a hydrocarbon group. Furthermore, X ⁻ is a halogen atom ion, R ⁴ OSO ₃ ⁻ (R ⁴ is a hydrocarbon group), or R ⁵ SO ₃ ⁻ (R ⁵ is a hydrocarbon group), OH ⁻ , HCO ₃ ⁻ , CO ₃ ^2−. , SO ₄ ²⁻ , R ⁶ COO ⁻ (R ⁶ is a hydrocarbon group), Y represents an oxy group or an imino group. ]

In the formula (1), the divalent organic group for R ² is not particularly limited, but is a divalent hydrocarbon group [for example, an alkylene group, an arylene group, a cycloalkylene group, or a group obtained by combining these groups. (For example, an alkylene-arylene group and the like) are preferable. In addition, as an alkylene group as a divalent organic group of R ² , for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, or the like has 1 to 10 carbon atoms. (Preferably 1 to 6, more preferably 1 to 4, particularly 1 to 3) alkylene group and the like. Examples of the arylene group include a phenylene group and a naphthylene group. Examples of the cycloalkylene group include a cyclohexylene group. Such a divalent hydrocarbon group is a substituent (for example, an alkyl group such as a methyl group or an ethyl group) within a range that does not impair the reactivity as a monomer and the antistatic property of a conductive polymer after polymerization. ). As the divalent organic group for R ² , an alkylene group can be suitably used among divalent hydrocarbon groups.

Examples of the hydrocarbon group for R ^{3a to} R ^3c include an alkyl group, an aryl group, and a cycloalkyl group. In the hydrocarbon groups of R ^{3a to} R ^3c , the alkyl group includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, and isopentyl. Examples thereof include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 4, particularly 1 to 3) such as a group and a hexyl group. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the cycloalkyl group include a cyclohexyl group. As the hydrocarbon group for R ^{3a to} R ^3c , an alkyl group can be suitably used.

R ^{3a to} R ^3c may be the same or different from each other. That is, R ^{3a to} R ^3c are all combinations of the same group (hydrogen atom or the same hydrocarbon group), any two are the same groups, and all are different groups.

As R < ^3a > -R <^3c>, it is preferable that at least any two (that is, all or any two) are the same or different combinations of hydrocarbon groups.

X ⁻ is a counter ion coordinated to a quaternary ammonium group (—N ⁺ R ^3a R ^3b R ^3c ). In such X ⁻ , examples of the halogen atom ion include chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), and fluorine ion (F ⁻ ). The hydrocarbon group as R ⁴ in R ⁴ OSO ₃ ^— may be any hydrocarbon group such as an alkyl group, an aryl group, a cycloalkyl group, etc., but an alkyl group (especially a methyl group, an ethyl group, Group) is preferred. Furthermore, the hydrocarbon group as R ⁵ in R ⁵ SO ₃ ^— may be any hydrocarbon group such as an alkyl group, an aryl group, and a cycloalkyl group, but an alkyl group (particularly a methyl group, Ethyl group and the like) and aryl groups (eg, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group and the like) are preferable. Further, R ⁶ COO ^- Examples of the hydrocarbon group as R ⁶ in an alkyl group, an aryl group, may be any hydrocarbon group such as a cycloalkyl group, an alkyl group (particularly, a methyl group, an ethyl group ) Is preferred.

In the present invention, X ⁻ represents Cl ⁻ , Br ⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , from the viewpoint of antistatic properties of the conductive polymer after polymerization. C ₂ H ₅ SO ₃ ⁻ and p—CH ₃ —C ₆ H ₄ —SO ₃ ^— are preferable, and Cl ⁻ and Br ⁻ (particularly Cl ⁻ ) can be preferably used.

  Y is an oxy group (—O—) or an imino group (—NH—). When Y is an oxy group, the quaternary ammonium salt-containing acrylic monomer represented by the formula (1) is a (meth) acrylic acid ester-based monomer having a quaternary ammonium salt-containing group (“fourth” Quaternary ammonium salt-containing acrylic acid ester monomer ”, and when Y is an imino group, the quaternary ammonium salt-containing acrylic monomer represented by the formula (1) is a quaternary ammonium salt. (Meth) acrylamide monomer having a salt-containing group (sometimes referred to as “quaternary ammonium salt-containing acrylamide monomer”).

  Accordingly, examples of the quaternary ammonium salt-containing acrylic monomer represented by the formula (1) include ammonium salts having an acryloyloxyalkyl group or an acryloylaminoalkyl group, and in particular, an acryloyloxyalkyl group or an acryloylamino group. An ammonium salt having an alkyl group can be suitably used together with the alkyl group.

  In the ammonium salt having an alkyl group together with such an acryloyloxyalkyl group or acryloylaminoalkyl group, the alkyl group bonded to the nitrogen atom in the quaternary ammonium salt is 1 to 3. In addition, when the alkyl group couple | bonded with the nitrogen atom in a quaternary ammonium salt is 1 or 2, the hydrogen atom has couple | bonded with the said nitrogen atom. When two or more alkyl groups are bonded to the nitrogen atom, the alkyl group may be only one type or two or more types may be combined.

More specifically, in the quaternary ammonium salt-containing acrylic monomer represented by the formula (1), a quaternary ammonium salt-containing acrylic ester system in which X ⁻ is Cl ⁻ and Y is an oxy group. Specific examples of the monomer (ie, ammonium chloride having an alkyl group together with an acryloyloxyalkyl group) are specifically exemplified. For example, acryloyloxyalkyl- such as acryloyloxyethyltrimethylammonium chloride and acryloyloxyethyltriethylammonium chloride Trialkylammonium chloride; acryloyloxyalkyl-dialkylammonium such as acryloyloxyethyldimethylammonium chloride and acryloyloxyethyldiethylammonium chloride Acryloyloxyalkyl-alkylammonium chloride such as acryloyloxyethylmethylammonium chloride, acryloyloxyethylmethylammonium chloride; acryloyloxyalkyl-dialkyl-alkylammonium chloride such as acryloyloxyethyldimethylethylammonium chloride, acryloyloxyethyldiethylmethylammonium chloride Chloride; acryloyloxyalkyl-alkyl-alkylammonium chlorides such as acryloyloxyethylmethylethylammonium chloride and acryloyloxyethylethylmethylammonium chloride.

X ⁻ represents another counter ion (for example, Br ⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₂ H ₅ SO ₃ ⁻ , p-CH ₃ —C _6). H ₄ -SO ₃ ^- quaternary ammonium salts containing acrylic acid ester monomer and a like) Y is a group (i.e., with acryloyloxyalkyl group, other than ammonium chloride having an alkyl group, acryloyloxy group In addition, examples of the ammonium salt having an alkyl group include those corresponding to the representative examples of the ammonium chloride having an alkyl group together with the acryloyloxyalkyl group.

Furthermore, in the quaternary ammonium salt-containing acrylic monomer represented by the formula (1), a quaternary ammonium salt-containing acrylamide monomer in which Y is an imino group (that is, an alkyl group together with an acryloylaminoalkyl group). Examples of the ammonium salt) include those corresponding to the quaternary ammonium salt-containing acrylate monomer in which Y is an oxy group. Specifically, X ^- is Cl ^- in it and Y is a quaternary ammonium salt-containing acrylamide monomer (i.e., with acryloyl aminoalkyl groups, ammonium chloride having an alkyl group) an imino group on, the representative examples For example, acryloylaminoalkyl-trialkylammonium chloride such as acryloylaminopropyltrimethylammonium chloride, acryloylaminopropyltriethylammonium chloride; acryloylaminoalkyl-dialkylammonium chloride such as acryloylaminopropyldimethylammonium chloride, acryloylaminopropyldiethylammonium chloride; Acryloylaminopropylmethylammonium chloride, acryloylaminop Acryloylaminoalkyl-alkylammonium chloride such as propylethylammonium chloride; acryloylaminoalkyl-dialkyl-alkylammonium chloride such as acryloylaminopropyldimethylethylammonium chloride, acryloylaminopropyldiethylmethylammonium chloride; acryloylaminopropylmethylethylammonium chloride; Examples include acryloylaminoalkyl-alkyl-alkylammonium chloride such as acryloylaminopropylethylmethylammonium chloride. X ⁻ represents another counter ion (for example, Br ⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₂ H ₅ SO ₃ ⁻ , p-CH ₃ —C _6). A quaternary ammonium salt-containing acrylamide monomer that is H ₄ —SO ₃ ^— or the like (that is, an ammonium salt having an alkyl group with an acryloylaminoalkyl group other than an ammonium chloride having an alkyl group together with an acryloylaminoalkyl group) In the same manner, those corresponding to the representative examples of ammonium chloride having an alkyl group together with the above acryloylaminoalkyl group may be mentioned.

  The conductive polymer is not particularly limited as long as it is a conductive polymer having at least the quaternary ammonium salt-containing acrylic monomer as a monomer component. For example, only the quaternary ammonium salt-containing acrylic monomer is used as a monomer component. The conductive polymer may be a quaternary ammonium salt-containing acrylic monomer and a monomer that can be copolymerized with the quaternary ammonium salt-containing acrylic monomer (copolymerizable monomer). A conductive polymer as a component is preferred. Such a copolymerizable monomer is not particularly limited as long as it is a monomer that can be copolymerized with a quaternary ammonium salt-containing acrylic monomer, but (meth) acrylic acid ester (acrylic acid ester, methacrylic acid ester) may be used. Preferably used. As such (meth) acrylic acid ester, (meth) acrylic acid alkyl ester (acrylic acid alkyl ester, methacrylic acid alkyl ester) can be preferably used. As for (meth) acrylic acid ester, only 1 type may be used and 2 or more types may be used in combination.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate , Undecyl (meth) acrylate, dodecyl (meth) acrylate, ( T) Decyl acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, (meta ) Eicosyl acrylate.

  Moreover, as (meth) acrylic acid ester other than (meth) acrylic acid alkyl ester, for example, it has an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate ( And (meth) acrylic acid ester and (meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate.

  Furthermore, in the copolymerizable monomer, as the copolymerizable monomer other than (meth) acrylic acid ester, various other copolymerizable monomers such as other monoethylenically unsaturated monomers and polyfunctional monomers can be used. Can be used. Other monoethylenically unsaturated monomers include, for example, monoethylenically unsaturated monomers having a polar group (polar group-containing copolymerizable monomers) and monoethylenically unsaturated monomers having no polar group And monomers (polar group-free copolymerizable monomers). Examples of the polar group-containing copolymerizable monomer include carboxyl group-containing monomers such as (meth) acrylic acid (acrylic acid, methacrylic acid), itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid, or anhydrides thereof. Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; Amide group-containing monomers such as methacrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide; Aminoethyl acrylate, dimethacrylate Amino group-containing monomers such as tilaminoethyl and t-butylaminoethyl (meth) acrylate; glycidyl group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; acrylonitrile and methacrylo Cyano group-containing monomers such as nitriles; N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, Examples thereof include heterocyclic-containing vinyl monomers such as N-vinylpyrrole, N-vinylimidazole, and N-vinyloxazole. As the polar group-containing copolymerizable monomer, a carboxyl group-containing monomer such as acrylic acid or its anhydride is suitable.

  Furthermore, polar group-free copolymerizable monomers include, for example, vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins such as ethylene, butadiene, isoprene and isobutylene; Dienes; Vinyl ethers such as vinyl alkyl ethers; Vinyl chloride; (Meth) acrylic acid alkoxyalkyl monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; Imido groups such as cyclohexylmaleimide and isopropylmaleimide Containing monomers and the like.

  In the copolymerizable monomer, examples of the polyfunctional monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methanetri (meth) acrylate , Allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di (meth) acrylate, hex Such distearate (meth) acrylate.

  In the conductive polymer, the proportion of the quaternary ammonium salt-containing acrylic monomer is 1% by weight or more (1 to 100% by weight) based on the total amount of the monomer components depending on the properties of the conductive polymer such as conductivity and physical properties. %) Can be appropriately selected. In the present invention, the ratio of the quaternary ammonium salt-containing acrylic monomer is 5 to 80% by weight (preferably 10 to 60% by weight, more preferably 10 to 40% by weight) based on the total amount of the monomer components. Is preferred. When the ratio of the quaternary ammonium salt-containing acrylic monomer is less than 5% by weight based on the total amount of the monomer components, the antistatic property is lowered, whereas when it exceeds 80% by weight, the durability is lowered.

  Further, when (meth) acrylic acid ester [particularly, (meth) acrylic acid alkyl ester] is used as the copolymerizable monomer, the proportion of (meth) acrylic acid ester is not particularly limited, but the monomer component It is desirable to select from the range of 10 to 95% by weight (preferably 20 to 60% by weight) based on the total amount.

  Further, when a polar group-containing copolymerizable monomer [particularly, a carboxyl group-containing monomer or its anhydride, among them (meth) acrylic acid] is used as the copolymerizable monomer, the polar group-containing copolymerizable monomer is used. The ratio of the monomer is desirably selected from the range of 1 to 30% by weight (preferably 2 to 20% by weight) with respect to the total amount of the monomer components.

  Furthermore, the ratio of other monomers (such as non-polar group-containing copolymerizable monomers and polyfunctional monomers) as the copolymerizable monomer is not particularly limited, and is 30% by weight or less based on the total amount of the monomer components. It can select suitably from the range of (0-30 weight%).

  The conductive polymer can be prepared by a known preparation method. Specifically, using the monomer component (quaternary ammonium salt-containing acrylic monomer, copolymerizable monomer, etc.), a known polymerization method (for example, solution polymerization method, emulsion polymerization method, suspension polymerization method, By using a bulk polymerization method or the like, a conductive polymer can be prepared. In preparing the conductive polymer, a polymerization initiator (such as a radical polymerization initiator), a chain transfer agent, a solvent, and an emulsifier can be used depending on the polymerization method and the like. Such polymerization initiators, chain transfer agents, solvents, emulsifiers and the like can be appropriately selected from known components and used. Further, the amount used is not particularly limited.

  The antistatic treatment agent that forms the antistatic treatment layer may contain a curing agent (or a crosslinking agent) as necessary, together with the conductive polymer. Therefore, the antistatic treatment layer may be formed of only a conductive polymer, or may be formed by curing or cross-linking the conductive polymer with a curing agent. Thus, when the conductive polymer is cured to form the antistatic treatment layer, the conductive polymer includes a monomer component, a polar group-containing copolymerizable monomer (particularly a carboxyl group-containing monomer such as acrylic acid). It is important that a monomer or its anhydride, especially acrylic acid) is used. By using a polar group-containing copolymerizable monomer as a monomer component, a polar group can be introduced into the conductive polymer. Therefore, the conductive polymer can be cured or crosslinked using the polar group as a crosslinking point. it can.

  As the curing agent (or crosslinking agent), an epoxy crosslinking agent, an isocyanate crosslinking agent, a metal chelate crosslinking agent, a metal alkoxide crosslinking agent, a metal salt crosslinking agent, a peroxide crosslinking agent, an oxazoline crosslinking agent, Examples include an aziridine-based crosslinking agent, a melamine-based crosslinking agent, a urea-based crosslinking agent, an amino-based crosslinking agent, a carbodiimide-based crosslinking agent, and a coupling agent-based crosslinking agent (such as a silane coupling agent). A hardening | curing agent can be used individually or in combination of 2 or more types. As the crosslinking agent, an epoxy crosslinking agent or an isocyanate crosslinking agent (particularly an epoxy crosslinking agent) can be suitably used. Specifically, the epoxy crosslinking agent is not particularly limited as long as it is an epoxy compound having two or more epoxy groups in the molecule. For example, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, glycerin diglycidyl. Ether, diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane In addition to 1,6-hexanediol diglycidyl ether, various epoxy resins can be used. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, diphenylmethane diisocyanate, a diphenylmethane diisocyanate double product, a reaction product of trimethylolpropane and tolylene diisocyanate, and trimethylolpropane. And the reaction product of hexamethylene diisocyanate, polyether polyisocyanate, polyester polyisocyanate and the like.

  In addition to the above components (conductive polymer, crosslinking agent, etc.), the antistatic treatment agent contains various additives (for example, antioxidants, anti-aging agents, ultraviolet absorbers, colorants, etc.) as necessary. It may be.

  As the antistatic treatment agent containing such a conductive polymer, a commercial product such as “Bondip PA-100” (manufactured by Konishi Co., Ltd.) can be used.

  Although it does not restrict | limit especially as thickness of an antistatic treatment layer, For example, it is 0.01-5 micrometers (preferably 0.05-3 micrometers, More preferably, it is 0.1-2 micrometers). If the thickness of the antistatic treatment layer is smaller than 0.01 μm, sufficient antistatic effect may not be obtained. On the other hand, if the thickness is larger than 5 μm, it is excessive quality and economically disadvantageous.

  The antistatic treatment layer can be formed by applying an antistatic treatment agent containing the conductive polymer to a predetermined surface of a substrate and drying or curing as necessary.

  The antistatic treatment layer may have either a single layer or a multilayer. Moreover, the antistatic treatment layer may be formed on the base material via another layer as long as the effects of the present invention are not impaired.

  In addition, when the antistatic process layer is formed in both surfaces of a base material, the adhesive layer should just be formed on at least one antistatic process layer. That is, when the pressure-sensitive adhesive sheet for removing a solvent-containing material has a structure having an antistatic treatment layer on both sides of a base material, “adhesive layer / antistatic treatment layer / base material / antistatic treatment layer / adhesive” It may have a layer configuration of “layer” or a layer configuration of “antistatic treatment layer / base material / antistatic treatment layer / adhesive layer”.

[Base material]
In the pressure-sensitive adhesive sheet for removing a solvent-containing material of the present invention, the substrate is not particularly limited. For example, when it is desired to avoid mixing of dust and foreign matter, a polyolefin film such as a polyethylene film or a polypropylene film; a polyethylene terephthalate film or the like A plastic film such as a polyester film can be suitably used without the risk of generating paper dust. Note that paper or the like can also be used as the base material when used simply for cleaning the roll. For the purpose of removing the paste and ink on the uneven surface, a foam made of polyurethane, polyethylene, EPDM (ethylene-propylene-diene rubber) or the like can also be suitably used as the substrate. Furthermore, depending on the application, it is also possible to use a nonwoven fabric, cloth, metal foil, or the like as the base material.

  The thickness of the substrate is not particularly limited and can be appropriately set in consideration of strength, workability, etc. Generally, it is about 10 to 500 μm (preferably 12 to 200 μm, more preferably 15 to 100 μm). is there. When the base material is a foam, the thickness of the base material is generally several mm to several tens mm.

  The substrate may have any form of a single layer or a multilayer. The substrate may be subjected to appropriate known or conventional surface treatment such as physical treatment such as corona discharge treatment or plasma treatment, chemical treatment such as undercoating treatment or back treatment, as necessary. In addition, the base material may contain additives such as an antioxidant, an anti-aging agent, an ultraviolet absorber, a plasticizer, a softening agent, a colorant, an antistatic agent, and a filler as necessary.

[Adhesive layer]
In the solvent-containing material-removing pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited, and known pressure-sensitive adhesives (for example, acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, Vinyl alkyl ether-based adhesive, polyester-based adhesive, polyamide-based adhesive, urethane-based adhesive, fluorine-based adhesive, styrene-diene block copolymer-based adhesive, and the like. An adhesive can be used individually or in combination of 2 or more types.

  In the present invention, as the pressure-sensitive adhesive, from the viewpoint of further improving the cleaning performance and solvent absorption, (A) a carboxyl group-containing acrylic polymer, (B) an amine compound containing a plurality of hydroxyl groups (“poly” A pressure-sensitive adhesive composition containing the (C) polyisocyanate compound may be suitably used. In such a pressure-sensitive adhesive, the carboxyl group-containing acrylic polymer (A) can be used as a base polymer (a basic component of the pressure-sensitive adhesive). The polyhydroxyamine compound (B) can be used as a curing aid (crosslinking aid). Furthermore, the polyisocyanate compound (C) can be used as a curing agent (crosslinking agent). That is, in the present invention, the carboxyl group-containing acrylic polymer (A) as the base polymer is obtained from the polyisocyanate compound (C) as the curing agent and the polyhydroxyamine compound (B) as the curing aid. It can be cured by crosslinking with heat during drying.

((A) carboxyl group-containing acrylic polymer)
The carboxyl group-containing acrylic polymer (A) is not particularly limited as long as it is an acrylic polymer containing at least one carboxyl group in the molecule. In the carboxyl group-containing acrylic polymer (A), the number of carboxyl groups contained in the molecule is not particularly limited as long as it is at least one, and the adhesive strength, cohesive strength, and cleaning of the adhesive sheet for removing solvent-containing materials are not limited. It can be appropriately selected according to performance, solvent absorption, type of paste (ink) to be removed, and the like. The carboxyl group-containing acrylic polymer (A) can be used alone or in combination of two or more.

  As the carboxyl group-containing acrylic polymer (A), for example, at least (meth) acrylic acid alkyl ester (acrylic acid alkyl ester, methacrylic acid alkyl ester) can be copolymerized with the (meth) acrylic acid alkyl ester. It is possible to use a copolymer having such a carboxyl group-containing monomer (carboxyl group-containing copolymerizable monomer) as a monomer component.

  Although it does not restrict | limit especially as (meth) acrylic-acid alkylester, (meth) acrylic-acid alkylester whose carbon number of an alkyl group is 1-20 (preferably 1-18, More preferably, 2-10) is suitable. Can be used. Specifically, as the (meth) acrylic acid alkyl ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid Butyl, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, (meth ) Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, ( (Meth) acrylic acid isodecyl, (meth) acrylic acid undecyl, (meth) acrylic acid Decyl, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate And (meth) acrylic acid alkyl esters such as eicosyl (meth) acrylate. The (meth) acrylic acid alkyl ester can be used alone or in admixture of two or more.

  Moreover, the carboxyl group-containing copolymerizable monomer is not particularly limited as long as it is a monomer component that can be copolymerized with (meth) acrylic acid alkyl ester and contains at least one carboxyl group in the molecule. Examples thereof include (meth) acrylic acid (acrylic acid, methacrylic acid), itaconic acid, maleic acid, fumaric acid, and crotonic acid. In addition, acid anhydrides of these carboxyl group-containing copolymerizable monomers (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride) should also be used as carboxyl group-containing copolymerizable monomers. Is possible. The carboxyl group-containing copolymerizable monomers can be used alone or in combination of two or more. As the carboxyl group-containing copolymerizable monomer, (meth) acrylic acid is preferable, and acrylic acid can be particularly preferably used.

  In the present invention, if necessary, a monomer (copolymerizable monomer) that can be copolymerized with a (meth) acrylic acid alkyl ester or a carboxyl group-containing copolymerizable monomer may be used in combination. . Examples of such copolymerizable monomers include cyano group-containing monomers such as (meth) acrylonitrile (acrylonitrile, methacrylonitrile); vinyl esters such as vinyl acetate and vinyl propionate; styrene, α-methylstyrene, vinyl Styrene monomers such as toluene; epoxy group-containing monomers such as glycidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Hydroxyl group-containing monomers; alkoxy group-containing monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; olefin monomers such as ethylene, propylene, isoprene and butadiene; methyl vinyl ether, ethyl vinyl ether Vinyl ether monomers such as ruthenium; amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide; amino group-containing monomers such as N, N-dimethylaminoethyl (meth) acrylate; halogens such as vinyl chloride Atom-containing monomers; (meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid cyclohexyl; (meth) acrylic acid aryl esters such as phenyl (meth) acrylate, and the like. Examples of the copolymerizable monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, Polyfunctional monomers such as divinylbenzene, butyl di (meth) acrylate, and hexyl di (meth) acrylate can also be used. A copolymerizable monomer can be used individually or in combination of 2 or more types. As the copolymerizable monomer, cyano group-containing monomers and vinyl esters are preferable, and acrylonitrile can be particularly preferably used.

  In addition, each ratio of (meth) acrylic acid alkyl ester, carboxyl group-containing copolymerizable monomer, and copolymerizable monomer is the type of paste (ink) to be removed (type of solid content and type of solvent) The (meth) acrylic acid alkyl ester is, for example, about 40 to 98% by weight (preferably 50 to 95% by weight) as a proportion of all monomer components, and the carboxyl group-containing copolymer The monomer content is about 0.5 to 15% by weight (preferably 1 to 10% by weight), and the copolymerizable monomer is about 0 to 50% by weight (preferably 2 to 40% by weight).

  The carboxyl group-containing acrylic polymer (A) can be prepared by a known or common polymerization method. Specifically, the polymerization method for obtaining the carboxyl group-containing acrylic polymer (A) includes a solution polymerization method, an emulsion polymerization method and a bulk polymerization performed using a polymerization initiator such as an azo compound or a peroxide. Examples thereof include a polymerization method performed by irradiating light or radiation using a photoinitiator, and a polymerization method using a polymerization initiator that decomposes to generate radicals (radical polymerization method) is preferable. The polymerization initiator is not particularly limited, and can be appropriately selected from known or commonly used ones such as 2,2′-azobisisobutyronitrile and 2,2′-azobis. Isovaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methyl) Butyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4,4-trimethylpentane, dimethyl-2,2′-azobis (2-methylpropio) Azo polymerization initiators such as benzoate; benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumylpa And peroxide polymerization initiators such as oxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, and the like. In the case of solution polymerization, it is preferable to use an oil-soluble polymerization initiator, which can be used singly or in combination of two or more. What is necessary is just the usage-amount, for example, can be selected from the range of 0.01-1 weight part with respect to 100 weight part of all the monomer components.

  In the polymerization, a chain transfer agent may be used. In solution polymerization, various common solvents can be used. Examples of such solvents include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane Organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone. A solvent can be used individually or in combination of 2 or more types.

((B) polyhydroxyamine compound)
The polyhydroxyamine compound (B) is not particularly limited as long as it is an amine compound having at least two hydroxyl groups (particularly alcoholic hydroxyl groups) in the molecule. Further, in the polyhydroxyamine compound (B), the number of nitrogen atoms contained in the molecule is not particularly limited, and can be appropriately selected according to the type of polyisocyanate compound (C) and the ratio thereof. . A polyhydroxyamine type compound (B) can be used individually or in combination of 2 or more types.

  Specifically, in the polyhydroxyamine compound (B), for example, the polyhydroxyamine compound (B) having one nitrogen atom in the molecule includes diethanolamine, dipropanolamine, diisopropanolamine, N-methyl. Dialcohol amines such as diethanolamine, N-methyldiisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-butyldiethanolamine, N-butyldiisopropanolamine; triethanolamine, tripropanolamine, triisopropanolamine Trialcoholamines such as

（式（２）中、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰は、同一又は異なって、それぞれ水素原子又は［−（Ｒ¹¹Ｏ）_m（Ｒ¹²Ｏ）_n−Ｈ］を示す。ここで、Ｒ¹¹、Ｒ¹²は、異なって、それぞれアルキレン基を示す。ｍ、ｎは０以上の整数であり、同時に０にならない。また、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰のうち少なくとも２つは［−（Ｒ¹¹Ｏ）_m（Ｒ¹²Ｏ）_n−Ｈ］である。さらに、Ｚは２価の炭化水素基を示し、ｐは１以上の整数である。） Moreover, as a polyhydroxyamine type compound (B) which has two nitrogen atoms in a molecule | numerator, the polyhydroxyamine type compound as shown by following formula (2) is mentioned.

(In the formula (2), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or [— (R ¹¹ O) _m (R ¹² O) _n —H]. R ¹¹ and R ¹² are different and each represents an alkylene group, m and n are integers of 0 or more and do not simultaneously become 0. Also, at least of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ Two are [— (R ¹¹ O) _m (R ¹² O) _n —H], and Z represents a divalent hydrocarbon group, and p is an integer of 1 or more.)

In the formula (2), examples of the alkylene group represented by R ¹¹ and R ¹² include alkylene groups having about 1 to 6 carbon atoms such as methylene, ethylene, propylene, trimethylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. (Preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms). The alkylene group may have a linear or branched form. As the alkylene group for R ¹¹ and R ¹² , an ethylene group or a propylene group can be suitably used.

Further, m and n are not particularly limited as long as they are integers of 0 or more. For example, at least one of m and n can be selected from a range of about 0 to 20 (preferably 1 to 10). As m and n, either one is 0 and the other is an integer of 1 or more (particularly 1) in many cases. In addition, although m and n do not become 0 at the same time, when m and n become 0 at the same time, R ^{7 to} R ¹⁰ indicate hydrogen atoms.

  Z represents a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group. The alkylene group for Z may be linear or branched. Moreover, either saturated or unsaturated may be sufficient. Examples of the alkylene group for Z include an alkylene group having about 1 to 6 carbon atoms such as methylene, ethylene, propylene, trimethylene and tetramethylene groups (preferably an alkylene group having 1 to 4 carbon atoms, more preferably 2 or 2 carbon atoms). 3 alkylene groups). Examples of the cycloalkylene group include cycloalkylene groups having about 5 to 12 members such as 1,2-cyclohexylene group, 1,3-cyclohexylene group, and 1,4-cyclohexylene group. As the arylene group, for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group and the like can be used.

  Although p will not be restrict | limited especially if it is an integer greater than or equal to 1, For example, it can select from the range of an integer of 1-10, Preferably it is an integer of 1-6 (more preferably 1-4).

  More specifically, examples of the polyhydroxyamine compound (B) represented by the formula (2) include N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, N, N. , N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxyethyl) trimethylenediamine, N, N, N ′, N′-tetrakis (2 -Hydroxypropyl) trimethylenediamine, ethyleneoxypolyoxyethylene condensate, ethylenediamine polyoxypropylene condensate, ethylenediamine polyoxyethylene-polyoxypropylene condensate, etc. can do. As such a polyhydroxyamine compound (B), for example, trade name “EDP-300”, trade name “EDP-450”, trade name “EDP-1100”, trade name “Pluronic” (above, Asahi Denka) (Commercially available) can be used.

  In addition, in this invention, it is also possible to use the amine compound which has multiple other reactive functional groups other than a hydroxyl group with a polyhydroxyamine compound (B).

((C) polyisocyanate compound)
The polyisocyanate compound (C) is not particularly limited as long as it is an isocyanate compound having at least two isocyanate groups in the molecule. Further, in the polyisocyanate compound (C), the number of isocyanate groups contained in the molecule is not particularly limited as long as it is at least two, and the type and ratio of the carboxyl group-containing acrylic polymer (A), solvent The content can be appropriately selected according to the adhesive strength, cohesive strength, cleaning performance, solvent absorption amount, type of paste (ink) to be removed, and the like. Examples of the polyisocyanate compound (C) include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, araliphatic polyisocyanates, and the like. Polyisocyanate compounds (C) can be used alone or in combination of two or more.

  Examples of the aliphatic polyisocyanate include 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, and 3-methyl-1. , 5-pentane diisocyanate, aliphatic diisocyanates such as lysine diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, Alicyclic diisocyanates such as hydrogenated tetramethylxylene diisocyanate are included.

  Examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4'-diphenylmethane. Diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3 , 3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1 , 4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate Anate etc. are included.

  Examples of the araliphatic polyisocyanate include araliphatic diisocyanates such as xylylene-1,4-diisocyanate and xylylene-1,3-diisocyanate.

  Further, as the polyisocyanate compound (C), the above-exemplified aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, duplex or trimer by araliphatic polyisocyanate, reaction product Products or polymers (for example, diphenylmethane diisocyanate dimers and trimers, reaction products of trimethylolpropane and tolylene diisocyanate, reaction products of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, poly Ether polyisocyanate, polyester polyisocyanate, etc.) can also be used.

  In addition, in this invention, crosslinking agents (for example, a polyfunctional melamine compound, a polyfunctional epoxy compound, etc.) other than a polyisocyanate type compound can be used with a polyisocyanate type compound (C).

  In such a pressure-sensitive adhesive composition, the content of each component [carboxyl group-containing acrylic polymer (A), polyhydroxyamine compound (B), polyisocyanate compound (C)] is not particularly limited. The content ratio of the polyhydroxyamine compound (B) is, for example, 0.1 to 50 parts by weight (preferably 1 to 30 parts by weight, more preferably 100 parts by weight of the carboxyl group-containing acrylic polymer (A). Can be selected from the range of 5 to 20 parts by weight. When the content ratio of the polyhydroxyamine compound (B) is less than 0.1 parts by weight with respect to 100 parts by weight of the carboxyl group-containing acrylic polymer (A), the time required for aging becomes long. On the other hand, when the amount is more than 50 parts by weight, the cohesive force of the pressure-sensitive adhesive may be reduced or the adherend may be contaminated.

  The content ratio of the polyisocyanate compound (C) is, for example, 5 to 50 parts by weight (preferably 8 to 40 parts by weight, more preferably 100 parts by weight of the carboxyl group-containing acrylic polymer (A). 10 to 30 parts by weight). When the content ratio of the polyisocyanate compound (C) is less than 5 parts by weight with respect to 100 parts by weight of the carboxyl group-containing acrylic polymer (A), the cohesive force of the pressure-sensitive adhesive is low and the pressure-sensitive adhesive force is high. When the amount is more than 50 parts by weight, the adhesive strength is lowered.

Incidentally, polyhydroxyamine compound (B), and the proportion of the polyisocyanate compound (C), the content of hydroxyl groups according to the polyhydroxy amine compound _(B) (M B) (mol) Further, the ratio of the isocyanate group content (M _C ) (mol) of the polyisocyanate compound (C) may have the following relationship. With such a ratio, even more excellent cohesiveness can be exhibited.
(M _C ) / (M _B ) = 0.1-100 (preferably 0.5-70, more preferably 1-50)

  The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer includes various additives, for example, tackifiers [for example, terpene resins (terpene resins, terpene phenol resins, aromatic modified terpene resins, hydrogenated terpene resins, etc.), Petroleum resin (aliphatic, aromatic, alicyclic), rosin resin (rosin, hydrogenated rosin ester, etc.), coumarone / indene resin, phenolic resin, styrene resin, etc.], various stabilizers (oxidation) Inhibitors, anti-aging agents, UV absorbers, etc.), plasticizers, softeners, colorants, antistatic agents, fillers, surfactants, foaming agents and the like may be included.

  The thickness of the pressure-sensitive adhesive layer can be arbitrarily set within the range in which the above-described characteristics of the present invention are obtained, and is, for example, about 1 to 100 μm (preferably 3 to 50 μm, more preferably 5 to 30 μm).

  The pressure-sensitive adhesive layer is formed on at least one surface of the substrate. The pressure-sensitive adhesive layer can be formed using a known method for forming a pressure-sensitive adhesive layer. Specifically, a method of forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive on an antistatic treatment layer formed on a predetermined surface of a substrate, drying and / or curing, or a method of forming a pressure-sensitive adhesive on a separator. A pressure-sensitive adhesive layer is formed using a method of forming a pressure-sensitive adhesive layer by applying an adhesive and then transferring the pressure-sensitive adhesive layer onto an antistatic treatment layer formed on a predetermined surface of a substrate. Can be formed on at least one surface of the substrate via an antistatic treatment layer.

  The pressure-sensitive adhesive layer may have either a single layer or multiple layers. Further, the pressure-sensitive adhesive layer may be formed on the antistatic treatment layer via another layer within a range not impairing the effects of the present invention.

  In addition, when the adhesive layer is formed in both surfaces of a base material, at least one adhesive layer should just be formed on the base material through the antistatic treatment layer. That is, when the pressure-sensitive adhesive sheet for removing a solvent-containing material has a structure having pressure-sensitive adhesive layers on both sides of a base material, “pressure-sensitive adhesive layer / antistatic treatment layer / base material / antistatic treatment layer / pressure-sensitive adhesive layer” Or a layer structure of “adhesive layer / base material / antistatic treatment layer / adhesive layer”.

[Solvent-containing adhesive sheet]
The pressure-sensitive adhesive sheet for removing a solvent-containing material of the present invention comprises a base material and an acrylic monomer having a group containing a quaternary ammonium salt formed on at least one surface of the base material. An antistatic treatment layer (sometimes referred to as “quaternary ammonium salt-containing antistatic treatment layer”) formed of an antistatic treatment agent containing a conductive polymer, and formed on the antistatic treatment layer. And a pressure-sensitive adhesive layer (sometimes referred to as “solvent-containing material removal pressure-sensitive adhesive layer”). That is, the solvent-containing material removal pressure-sensitive adhesive sheet of the present invention has a structure in which a solvent-containing material removal pressure-sensitive adhesive layer is formed on at least one surface of a substrate via a quaternary ammonium salt-containing antistatic treatment layer. have. The solvent-containing material-removing pressure-sensitive adhesive sheet has a structure in which a pressure-sensitive adhesive layer is formed on one side of the base material (single-sided pressure-sensitive adhesive sheet with a base material), and a structure in which pressure-sensitive adhesive layers are formed on both sides of the base material. Any of an adhesive sheet (double-sided adhesive sheet with a base material) may be sufficient. The pressure-sensitive adhesive layer may be protected by a release film (release liner).

  In addition, when the said adhesive sheet for solvent containing material removal is a single-sided adhesive sheet with a base material, the adhesive layer formed in the single side | surface of a base material through the quaternary ammonium salt containing antistatic process layer is a solvent containing This is an adhesive layer for removing objects. On the other hand, when the pressure-sensitive adhesive sheet for removing a solvent-containing material is a double-sided pressure-sensitive adhesive sheet with a substrate, the pressure-sensitive adhesive layer formed on both surfaces of the substrate via a quaternary ammonium salt-containing antistatic treatment layer removes the solvent-containing material. The pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer formed on one side of the substrate via a quaternary ammonium salt-containing antistatic treatment layer, and the other side. The pressure-sensitive adhesive layer formed may be a pressure-sensitive adhesive layer that is not a solvent-containing material-removing pressure-sensitive adhesive layer.

  The pressure-sensitive adhesive sheet for removing a solvent-containing material of the present invention has a structure in which a pressure-sensitive adhesive layer for removing a solvent-containing material is formed on one side of a substrate via a quaternary ammonium salt-containing antistatic treatment layer. Preferably it is.

  The pressure-sensitive adhesive sheet for removing a solvent-containing material may have other layers (for example, an intermediate layer, an undercoat layer, etc.) as long as the effects of the present invention are not impaired. Specifically, between the base material and the quaternary ammonium salt-containing antistatic treatment layer, between the quaternary ammonium salt-containing antistatic treatment layer and the pressure-sensitive adhesive layer for solvent-containing material removal, for example, Layers such as a primer layer and an intermediate layer may be formed. Moreover, when the pressure-sensitive adhesive sheet for solvent-containing material removal has a configuration in which a pressure-sensitive adhesive layer for solvent-containing material removal is formed on one side of the base material via a quaternary ammonium salt-containing antistatic treatment layer, A back surface treatment layer may be formed on the back surface of the substrate (the surface on the opposite side to the surface on which the pressure-sensitive adhesive layer for removing the solvent-containing material is formed). Such a back surface treatment layer is a known or common back surface treatment agent (for example, a long chain alkyl release agent such as a long chain alkyl acrylate polymer or a long chain alkyl-modified polymer; an alkyl pendant release agent; a silicone release agent). A fluorine-based release agent, etc.).

  In this invention, the adhesive sheet for solvent content removal may be formed in the form wound by roll shape, and may be formed in the form by which the sheet | seat was laminated | stacked. That is, the adhesive sheet for removing a solvent-containing material of the present invention can have a form such as a sheet form or a tape form. In addition, when the pressure-sensitive adhesive sheet for solvent-containing material removal has a form wound in a roll shape, for example, a pressure-sensitive adhesive layer such as a pressure-sensitive adhesive layer for solvent-containing material removal is placed on the back side of the separator or substrate. The adhesive sheet for solvent-containing material removal of the form wound by the roll shape is producible by winding in a roll shape in the state protected by the formed peeling process layer.

  The pressure-sensitive adhesive sheet for removing the solvent-containing material is formed on at least one surface of the base material using an antistatic treatment layer containing a quaternary ammonium salt, by using a known or common method such as a coating method, depending on the layer structure and the like. It can be manufactured by forming a pressure-sensitive adhesive layer for removing a solvent-containing material and, if necessary, forming an undercoat layer or a back treatment layer on a predetermined surface. In addition, application | coating of the antistatic processing agent containing the conductive polymer which has the acryl-type monomer which has group containing a quaternary ammonium salt at least as a monomer component, an adhesive composition, etc. is a conventional coater ( For example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater or the like can be used.

  In the pressure-sensitive adhesive sheet for removing a solvent-containing material of the present invention, since the pressure-sensitive adhesive layer has a structure formed on the base material via the quaternary ammonium salt-containing antistatic treatment layer, the back side of the screen printing plate The generation of static electricity can be further suppressed or prevented when removing the solvent-containing material such as the paste that is on the back. Therefore, the use of the solvent-containing material removal sheet of the present invention prevents the generation of static electricity without the need to leave static electricity in the cleaning unit of a screen printing machine. Efficiently contains solvent without causing problems such as pulling and repulsion between sheets, scattering of solvent-containing materials due to static electricity, worker discomfort due to static electricity shock, and adhesion of dust and dirt around by static electricity Things can be removed, and the yield and the operation rate of equipment can be improved.

  In particular, the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer for solvent-containing material removal) contains a carboxyl group-containing acrylic polymer (A), a polyhydroxyamine compound (B), and a polyisocyanate compound (C). When it is formed of the composition, the cleaning performance and the solvent absorption can be further improved. Moreover, since the hydroxyl group (hydroxyl group) of the polyhydroxyamine compound (B) and the isocyanate group of the polyisocyanate compound (C) react rapidly, the cohesive force that greatly affects the productivity is expressed. Aging time required for the process can be greatly reduced. That is, sufficient cohesive force can be exhibited even with short-time aging, and excellent cleaning performance and solvent absorption can be exhibited.

  In the present invention, the solvent-containing material to be removed is not particularly limited, and examples thereof include semi-solid materials that contain a solvent and are in a wet state, such as pastes, inks, glues, adhesives, and paints. Specifically, examples of the solvent-containing material include paste (ink) used for screen printing and ink attached to rolls of a printing machine such as an offset printing machine.

  The adhesive sheet for solvent-containing material removal absorbs the solvent contained in the paste attached to the back side of the screen plate or the ink attached to the rolls, for example, by sticking it to the back side of the screen plate or rolls. Thus, the paste or the like can be solidified. Accordingly, the pressure-sensitive adhesive sheet for removing a solvent-containing material of the present invention is, for example, a paste (ink) that is turned around on the back side of a screen printing plate, an ink attached to a roll of a printing press such as offset printing, or an ink jet of an inkjet printer. It is suitable for removing ink stains near the mouth. That is, the adhesive sheet for removing a solvent-containing material of the present invention can be suitably used as an adhesive sheet for cleaning a screen printing plate.

  Examples of the solvent contained in the solvent-containing material such as paste and ink include aliphatic hydrocarbons such as hexane, heptane and mineral spirits; alicyclic hydrocarbons such as cyclohexane; toluene, xylene, solvent naphtha, tetralin and dipentene. Aromatic alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, s-butyl alcohol, cyclohexyl alcohol, 2-methylcyclohexyl alcohol, tridecyl alcohol, etc .; methyl acetate, ethyl acetate, acetic acid Esters such as isopropyl and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, diacetone alcohol, isophorone, etc. Ketones; glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol; glycol ethers such as butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether; butyl cellosolve acetate, Examples include glycol ether esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate; water and the like. In the case of screen printing ink, medium boiling solvent (boiling point: about 120 to 230 ° C.) and high boiling point solvent (boiling point: about 230 to 320 ° C.) are often used. For example, diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether (For example, diethylene glycol monobutyl ether acetate / diethylene glycol monobutyl ether [9/1 (weight ratio)]) and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the following, “part” means “part by weight” and “%” means “% by weight”.

Example 1
A blend of a main product of a trade name “Bondip PA-100” (manufactured by Konishi Co., Ltd.) and a curing agent in a ratio of main agent: curing agent = 1: 1 (weight ratio), and a mixture of isopropyl alcohol and water. It was dissolved in a mixed solvent [isopropyl alcohol: water = 2: 1 (weight ratio)] to prepare a thermosetting antistatic treatment solution having a concentration of 1.7%.

  In addition, with respect to 100 parts (solid content) of a carboxyl group-containing acrylic copolymer [a copolymer of butyl acrylate / acrylonitrile / acrylic acid = 85: 15: 2.5 (weight ratio)], the trade name “ EDP-1100 (manufactured by Asahi Denka Co., Ltd., polyoxypropylene condensate of ethylenediamine as an amine compound containing a plurality of hydroxyl groups) ", product name" Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd., poly Isocyanate-based compound) "15 parts was added and mixed well to prepare a pressure-sensitive adhesive composition.

  One side of a polypropylene film (thickness: 40 μm) is subjected to corona discharge treatment, and the thermosetting antistatic treatment solution is applied to the corona discharge treatment surface using a wire bar and dried to prevent antistatic. After forming the treatment layer (thickness: 0.7 μm), the pressure-sensitive adhesive composition is applied on the antistatic treatment layer so that the thickness after drying is 8 μm, and the temperature is 90 ° C. A pressure-sensitive adhesive layer was formed by drying or curing for 3 minutes to prepare a pressure-sensitive adhesive sheet.

(Comparative Example 1)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the antistatic treatment layer was not formed. That is, a corona discharge treatment is performed on one side of a polypropylene film (thickness: 40 μm), and the same pressure-sensitive adhesive composition as in Example 1 is applied to this corona discharge treatment surface so that the thickness after drying becomes 8 μm. It was applied and dried or cured at a temperature of 90 ° C. for 3 minutes to form a pressure-sensitive adhesive layer, thereby preparing a pressure-sensitive adhesive sheet.

(Evaluation)
About each adhesive sheet obtained in Example 1 and Comparative Example 1, the surface resistivity, adhesive strength, and solvent absorption amount were determined by the following methods (surface resistivity measurement method, adhesive strength measurement method, solvent absorption amount measurement method). ) Was measured and evaluated. The results are shown in Table 1.

(Measurement method of surface resistivity)
According to JIS K6911, the resistivity (Ω) on the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet was measured. Specifically, the resistance value after 1 minute was measured at an applied voltage of 100V. However, the sample preparation and measurement atmosphere is 23 ° C. and 50% RH.

(Measurement method of adhesive strength)
A 20 × 100 mm pressure-sensitive adhesive sheet is pressure-bonded to a stainless steel plate (SUS430BA plate) as an adherend with a laminator, and the force required for the peeling (180 ° peeling, pulling speed 300 mm / min, 23 ° C., 50% RH) is measured. did.

(Measurement method of solvent absorption)
The adhesive sheet, cut to 20 x 50 mm and weighed in advance, is immersed in diethylene glycol monobutyl ether acetate, which is a solvent for screen printing, for 1 second and removed, and the solvent on the adhesive sheet surface is immediately wiped off with a waste cloth. The weight was measured again, and the increase in weight per unit area was calculated.

  From Table 1, it was confirmed that the pressure-sensitive adhesive sheet according to the example has excellent adhesive strength and solvent absorption, has a small surface resistivity on the surface of the pressure-sensitive adhesive layer, and has excellent antistatic properties. . Therefore, by providing a predetermined antistatic treatment layer between the base material and the pressure-sensitive adhesive layer, the surface resistivity on the surface of the pressure-sensitive adhesive layer can be effectively reduced without lowering the adhesive strength or the solvent absorption amount. It was confirmed that a pressure-sensitive adhesive sheet for removing a solvent-containing material exhibiting excellent antistatic properties can be obtained.

Claims (4)

A solvent-containing material-removing pressure-sensitive adhesive sheet having a structure in which a pressure-sensitive adhesive layer is formed on at least one surface of a substrate via an antistatic treatment layer, wherein the anti-static treatment layer comprises a quaternary ammonium salt. A pressure-sensitive adhesive sheet for removing a solvent-containing material, characterized in that it is formed of an antistatic treatment agent containing a conductive polymer containing at least an acrylic monomer having a containing group as a monomer component. The pressure-sensitive adhesive sheet for removing a solvent-containing material according to claim 1, wherein the antistatic treatment layer has a thickness of 0.01 to 5 µm. The pressure-sensitive adhesive layer is formed of (A) a carboxyl group-containing acrylic polymer, (B) an amine compound containing a plurality of hydroxyl groups, and (C) a pressure-sensitive adhesive composition containing a polyisocyanate compound. The pressure-sensitive adhesive sheet for removing a solvent-containing material according to claim 1 or 2. The pressure-sensitive adhesive sheet for removing a solvent-containing material according to any one of claims 1 to 3, which is used as a pressure-sensitive adhesive sheet for cleaning a screen printing plate.