TW201343853A - Adhesive composition, adhesive layer and adhesive sheet - Google Patents

Abstract

This invention provides an adhesive composition, an adhesive layer containing the adhesive composition and an adhesive sheet formed by forming an adhesive layer on a substrate. The adhesive composition comprises an acrylic acid-based polymer (A) and a polyoxyalkylene alkyl ether (B) with a molecular weight of 200 to 1000, wherein based on 100 parts by weight of the acrylic acid-based polymer (A), the content of the polyoxyalkylene alkyl ether (B) is 0.1 to 100 parts by weight.

Description

Adhesive composition, adhesive layer and adhesive sheet

The present invention relates to an adhesive sheet excellent in wettability, and an adhesive layer and an adhesive composition for the adhesive sheet.

The adhesive sheet has a gel-like soft adhesive layer on a substrate such as a plastic film or paper, and the adhesive layer is solid and exerts an adhesive force by wetting the adherend. That is, the adhesive layer is required to sufficiently wet the adherend. On the other hand, the adhesive layer needs to have a cohesive force (fixation) to the extent of peeling. Therefore, the adhesive sheet is designed in consideration of wettability and cohesive force as opposite characteristics.

Therefore, in general, when the adhesive sheet is bonded to the adherend, it is pressurized, and if it is heated in a state of being heated, it is applied so as to be in close contact with the adherend. When it is possible to pressurize or heat during construction as described above, even if the wettability of the adhesive tape is poor, it can be used, but in the case where the adherend is a minute component or a defect is caused by heating. This type of construction becomes difficult.

Further, as a problem in which the wettability of the adherend is a problem, it is conceivable that air bubbles enter between the adherend and the adhesive sheet. For example, it is known that when the film for decoration is laminated, in order to prevent the residual of the bubble, a convex protrusion is provided on the adhesive layer, or a concave stripe is formed to allow the bubble to escape, but the adhesion is not substantially improved. The wettability of the sheet.

As a method of improving the wettability of the adhesive sheet, it is known that the acrylic polymer constituting the adhesive layer is a graft polymer structure having an alkylene oxide on its side chain. That is, Patent Document 1 discloses a surface protective film in which an adhesive layer obtained by crosslinking an adhesive composition is formed on a support film, and the adhesive composition contains 51~ 100% by weight of a (meth)acrylic acid alkylene oxide adduct, and 0 to 49% by weight of a (meth)acrylic monomer other than the above, and 0 to 49% by weight of another polymerizable monomer as a monomer component ( A methyl) acrylic (co)polymer and a crosslinking agent. Further, Patent Document 2 discloses an adhesive material for re-peeling in which an adhesive layer obtained from a solvent-based re-peeling adhesive composition is formed on at least one surface of a support substrate, and the solvent-type re-peeling is used. The adhesive composition is characterized in that it is used in the formulation of a crosslinking agent and contains an adhesive polymer, and the adhesive polymer has a polymer structure having a glass transition temperature of 0 ° C or more and a raw material monomer as follows a graft and/or block polymer of a polymer structure of a component composition, wherein the raw material monomer component comprises an alkyl (meth)acrylate (A) having an alkyl group having 4 to 12 carbon atoms, and an alkylene oxide chain And/or the long-chain-containing monomer (B) having a long-chain alkyl group and the functional group-containing monomer (C) are essential components, and if necessary, other monomers (D) are contained.

However, in the invention described in Patent Document 2, even if it is a contact area of a narrow range of 4 cm × 4 cm, it takes 20 seconds or more until the entire fusion, and it does not have sufficient wettability.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2005-200540

Patent Document 2: Japanese Patent Laid-Open Publication No. 2009-227737

Accordingly, an object of the present invention is to provide an adhesive composition excellent in wettability, an adhesive layer, and an adhesive sheet using the same to solve the problem of the prior acrylic adhesive.

The inventors of the present invention conducted intensive studies to achieve the above object, and as a result, have found that the above problems can be solved by adhering a sheet which is formed on a substrate to form an adhesive composition as follows. Adhesive layer, the above adhesion The composition contains an acrylic polymer and a polyoxyalkylene alkyl ether having a molecular weight of 200 to 1000, and the content of the polyoxyalkylene alkyl ether is 0.1 to 100 by weight based on 100 parts by weight of the acrylic polymer. Share.

That is, in the present invention, the wettability of the adhesive can be improved by disposing a specific amount of polyoxyalkylene alkyl ether having a molecular weight of 200 to 1,000. In the present invention, the polyoxyalkylene alkyl ether is formulated to have a low rotational energy of the ether bond, so that the degree of rotational freedom of the molecule is high, and the wettability is improved due to the lower polarity of the terminal group. . Here, the wettability cannot be sufficiently improved by the polyoxyalkylene group having a hydroxyl group at both ends, and the reason is that the surface free energy of the hydroxyl group is high. Further, in the present invention, it is necessary to form a structure in which an alkyl group is bonded to at least one terminal of a polyoxyalkylene group. It may, for example, not be an aromatic substituent (phenyl or methylphenyl). The reason for this is considered to be that the substituent of the aromatic system has a large steric hindrance, and thus the degree of freedom of rotation of the molecule is lowered. Further, the molecular weight of the polyoxyalkylene alkyl ether must be from 200 to 1,000. The reason for this is considered to be that if the molecular weight is too high, the freezing point (flow point) becomes high, and thus the degree of freedom of rotation of the molecules is lowered, so that it is difficult to improve the wettability.

The present invention provides an adhesive composition comprising an acrylic polymer (A) and a polyoxyalkylene alkyl ether (B) having a molecular weight of 200 to 1000, and the polyoxyalkylene alkyl ether (B) The content is 0.1 parts by weight to 100 parts by weight based on 100 parts by weight of the acrylic polymer (A).

Particularly in the adhesive composition of the present invention, the above polyoxyalkylene alkyl ether (B) is preferably a polyoxypropylene alkyl ether. Further, the alkyl group constituting the above polyoxyalkylene alkyl ether (B) is preferably a methyl group, an ethyl group, a butyl group or a 2-ethylhexyl group.

Further, the present invention provides an alkyl (meth)acrylate having at least 80% by weight to 99.9% by weight of an alkyl group having 4 to 18 carbon atoms and 0.1% by weight to 20% by weight based on the acrylic polymer (A). The above adhesive composition characterized by containing a functional group monomer as a monomer component.

Moreover, the present invention provides the above-mentioned adhesive composition characterized by containing 1 part by weight to 10 parts by weight of the crosslinking agent (C) per 100 parts by weight of the acrylic polymer (A). especially Preferably, the crosslinking agent (C) is an isocyanate crosslinking agent.

Moreover, the present invention provides an adhesive sheet comprising the above adhesive composition and an adhesive sheet formed by forming the adhesive layer on a substrate.

The adhesive composition, the adhesive layer and the adhesive sheet of the present invention are superior in wettability to the conventional acrylic pressure-sensitive adhesive sheet. Therefore, the adhesive sheet of the present invention is not particularly pressurized even when it is bonded to the adherend, and can be sufficiently adhered to the adherend to sufficiently prevent the incorporation of air bubbles or the like. Therefore, it can be used as various adhesive sheets.

1‧‧‧adhesive body

2‧‧‧Test piece (adhesive sheet)

Fig. 1 is a schematic view showing a method of evaluating wettability in Examples.

Hereinafter, embodiments of the present invention will be described in detail.

The adhesive composition of the present invention contains 0.1 part by weight to 100 parts by weight of the polyoxyalkylene alkyl ether (B) having a molecular weight of 200 to 1,000 based on 100 parts by weight of the acrylic polymer (A).

(acrylic polymer (A))

In the present invention, the acrylic polymer (A) is not particularly limited as long as it is polymerized from a monomer component containing an acrylic monomer, and an acrylic polymer which is usually used in an adhesive composition can be used. The acrylic polymer (A) preferably has at least 80% by weight to 99.9% by weight of an alkyl group having 4 to 18 carbon atoms in terms of easy balance of adhesion, cohesiveness, and other adhesive properties. The (meth)acrylic acid alkyl ester and 0.1% by weight to 20% by weight of the functional group-containing monomer are used as a monomer component.

Specific examples of the alkyl (meth)acrylate having an alkyl group having 4 to 18 carbon atoms constituting the acrylic polymer (A) include butyl (meth)acrylate and isobutyl (meth)acrylate. Ester, tert-butyl (meth)acrylate, pentyl (metha)acrylate, amyl(metha)acrylate,(methyl)propene Isoamyl enoate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethyl hexyl (meth) acrylate, ( Ethyl methacrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, (methyl) Lauryl acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, (A) A (meth)acrylic acid alkyl ester such as a heptadecyl acrylate or an octadecyl (meth) acrylate. These may be used singly or in combination of two or more.

The content ratio of the alkyl (meth)acrylate having an alkyl group having 4 to 18 carbon atoms is preferably 80% by weight to 99.9% by weight, and more preferably 90% by weight to 99% by weight based on the total of the monomer components.

The functional group-containing single system constituting the acrylic polymer (A) imparts polarity or reactivity to the acrylic polymer, or reacts with the crosslinking agent described below to contribute to formation of a crosslinked structure, and examples thereof include a carboxyl group. Or a functional group-containing monomer having a functional group such as a hydroxyl group.

Specific examples of the functional group-containing monomer include carboxyl group-containing monomers such as (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid; and (meth)acrylic acid 2 -hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl methacrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxy decyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, acrylic acid [4-(hydroxyl) A hydroxyl group-containing monomer such as a hydroxyalkyl (meth)acrylate such as a cyclohexylmethyl ester.

Further, in the present invention, examples of the functional group-containing monomer include N-methylol acrylamide, N-methylol methacrylamide, N-(2-hydroxyethyl) acrylamide, and N. -(2-hydroxyethyl)methacrylamide, N-(2-hydroxypropyl)propenylamine, N-(2-hydroxypropyl)methacrylamide, N-(1-hydroxypropyl Acrylamide, N-(1-hydroxypropyl)methacrylamide, N-(3-hydroxypropyl)propenamide, N-(3-hydroxypropyl)methacrylamide, N- (2-hydroxyl Butyl) acrylamide, N-(2-hydroxybutyl)methacrylamide, N-(3-hydroxybutyl) acrylamide, N-(3-hydroxybutyl)methacrylamide, N-hydroxyalkyl (meth) acrylamide such as N-(4-hydroxybutyl) acrylamide or N-(4-hydroxybutyl)methacrylamide; glycidyl (meth)acrylate, (Ethylene methacrylate, methyl methacrylate, allylic glycidyl ether, etc.; , N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylolpropane (methyl) propylene a monomer having a guanamine group such as guanamine, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-vinyl carbamide; Amino group-containing monomer such as aminoethyl methacrylate, N,N-dimethylaminoethyl (meth)acrylate, and tert-butylaminoethyl (meth)acrylate; acrylonitrile, A a monomer having a cyano group such as acrylonitrile; diacetone (meth) acrylamide, diacetone (meth) acrylate, vinyl methyl ketone, vinyl ethyl , Acetyl, allyl acetate, vinyl acetate acetyl group of the monomer having a ketone; 2- isocyanatoethyl (meth) acrylate and the like Bing Xixi group containing monomer of an isocyanate group.

These functional group-containing monomers may be used singly or in combination.

The content of the functional group-containing monomer is preferably from 0.1% by weight to 20% by weight, and more preferably from 1% by weight to 10% by weight based on the total of the monomer components. When the content of the functional group-containing monomer is less than 0.1% by weight, it becomes difficult to obtain an effect of addition thereof, for example, crosslinking formation becomes insufficient, and cohesive force of the adhesive composition cannot be obtained, and the sheet is adhered when the article is fixed. Offset, or when the adhesive sheet is peeled off, the residue remains. On the other hand, when the content ratio of the functional group-containing monomer is more than 20% by weight, the cohesive force of the acrylic polymer is increased, so that the fluidity is lowered and the wettability is lowered.

In the present invention, in the monomer component constituting the acrylic polymer (A), a copolymerization property for adjusting the glass transition point or the adhesion of the acrylic polymer (A) may be additionally used within a range not impairing the effects of the present invention. Monomers, etc. Examples of such a copolymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate having a carbon number of less than 4 Alkyl alkyl (meth)acrylates; vinyl acetates such as vinyl acetate and vinyl propionate; aromatic vinyls such as styrene, substituted styrene (α-methylstyrene, etc.), vinyl toluene, etc. Base compound; cyclohexyl (meth)acrylate, cyclopentyl di(meth)acrylate, (meth)acrylic acid An alicyclic hydrocarbon (meth) acrylate such as an ester; an aromatic ring-containing (meth) acrylate such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate or benzyl (meth) acrylate; An olefin monomer such as ethylene, propylene, isoprene, butadiene or isobutylene; a halogen atom-containing monomer such as vinyl chloride or vinylidene chloride; methoxyethyl (meth)acrylate; Alkoxy-containing monomer such as ethoxyethyl acrylate; vinyl ether monomer such as methyl vinyl ether or ethyl vinyl ether; N-vinyl-2-pyrrolidone, N-(1) -methylvinyl)pyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperidone N-vinylpyrene , N-vinylpyrrole, N-vinylimidazole, N-vinyl Oxazole, N-vinyl Porphyrin, N-vinyl caprolactam, N-(methyl) propylene fluorenyl A monomer having a hetero ring such as a porphyrin or a tetrahydrofurfuryl (meth) acrylate.

In the present invention, as the copolymerizable monomer, a monomer having a plurality of functional groups in one molecule or a combination of two or more kinds as appropriate may be used alone. The polyfunctional monomer functions to improve the heat resistance or cohesiveness of the adhesive. Specific examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene. Alcohol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylic acid Mono or polyalkylene glycol di(meth)acrylate such as ester; neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(methyl) ) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, two Vinyl benzene, etc.

As the copolymerizable monomer, a monomer having an alkoxyalkylene group or a combination of two or more kinds thereof may be used alone. The alkoxyalkylene group-containing monomer functions to improve the heat resistance or cohesiveness of the adhesive. Specific examples of the alkoxyalkylene group-containing monomer include 3-(meth)acryloxypropyltrimethoxydecane and 3-(meth)acryloxypropyltriethoxy group. Decane, 3-(meth)acryloxypropylmethyldimethoxydecane, 3-(meth)acryloxypropylmethyldiethoxydecane, vinyltrimethoxydecane, etc. Methyl) propylene decyloxydecane derivative.

Such a copolymerizable monomer may be used singly or in combination of two or more kinds as appropriate. For example, the copolymerizable monomer may be used in an amount of 20% by weight or less (0% by weight to 20% by weight) based on the total monomer components, and is usually 15% by weight or less (0% by weight to 15% by weight), preferably 10% by weight or less (0% by weight to 10% by weight). The lower limit of the amount of use in the case of using a copolymerizable monomer is not particularly limited, and may be an amount that can achieve the purpose of use of the monomer. Usually, the amount of the copolymerizable monomer used is suitably 0.001% by weight or more based on the total monomer components.

The acrylic polymer (A) used in the present invention can be produced by polymerizing the above monomer components by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization or various radical polymerization. Further, the obtained acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer and the like.

Further, in the solution polymerization, for example, ethyl acetate, toluene or the like can be used as the polymerization solvent. The polymerization solvent can also be used in combination. As a specific solution polymerization example, the reaction is carried out under an inert gas stream such as nitrogen, and a polymerization initiator is added, usually at about 50 ° C to 70 ° C, 2 It is carried out under the reaction conditions of an hour or more (for example, about 5 hours to 30 hours).

The polymerization initiator, the chain transfer agent, the emulsifier, and the like used in the radical polymerization are not particularly limited, and can be appropriately selected and used. In addition, the weight average molecular weight of the following acrylic polymer can be controlled by the use amount of a polymerization initiator, a chain transfer agent, and reaction conditions, and can be suitably adjusted according to these types.

Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, and 2,2'-azobis. [2-(5-Methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'- Azobis(N,N'-dimethylideneisobutane), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine hydrate (Wako Pure Chemicals) Made by the company, VA-057) and other azo-based initiators; persulfate such as potassium persulfate or ammonium persulfate; di(2-ethylhexyl) peroxydicarbonate and di-dicarbonate (4- Tributylcyclohexyl)ester, di-second butyl peroxydicarbonate, tert-butyl peroxy neodecanoate, third hexyl peroxypivalate, tert-butyl peroxypivalate Oxidized dilaurin, di-n-octyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, bis(4-methylbenzhydryl) peroxide, peroxidation Starting of peroxides such as benzamidine, tert-butyl peroxybutyrate, 1,1-di(trihexylperoxy)cyclohexane, tert-butyl hydroperoxide, hydrogen peroxide, etc. Agent; group of persulfate and sodium bisulfite , A combination of a peroxide in combination with sodium ascorbate peroxidase and redox initiation of the redox agent, and the like, but is not limited to such.

The above polymerization initiator may be used singly or in combination of two or more. The content as a whole is preferably from 0.005 parts by weight to about 1 part by weight, more preferably 0.02 parts by weight, based on 100 parts by weight of all the monomer components. ~0.5 parts by weight or so.

Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, and 2-ethylhexyl thioglycolate. Ester, 2,3-dimercapto-1-propanol, and the like. The chain transfer agent may be used singly or in combination of two or more kinds, and the content as a whole is relative to all monomers. It is about 0.1 part by weight or less in 100 parts by weight.

Further, examples of the emulsifier used in the case of emulsion polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkyl. Anionic emulsifier such as sodium phenyl ether sulfate; nonionic emulsifier such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer, etc. . These emulsifiers may be used singly or in combination of two or more.

Further, examples of the reactive emulsifier include an emulsifier to which a radical polymerizable functional group such as a propenyl group or an allyl ether group is introduced, and specific examples thereof include Aqualon HS-10, HS-20, and KH-10. BC-05, BC-10, BC-20 (all of which are manufactured by Di-Industrial Pharmaceutical Co., Ltd.), Adeka Reasoap SE10N (manufactured by Adeka Co., Ltd.), and the like. Since the reactive emulsifier is incorporated into the polymer chain after polymerization, water resistance is improved and is preferred. The amount of the emulsifier used is preferably from 0.3 part by weight to 5 parts by weight per 100 parts by weight of the total of the monomer component, and more preferably from 0.5 part by weight to 1 part by weight in terms of polymerization stability or mechanical stability. Further, when the polymerization is carried out using an emulsifier corresponding to the polyoxyalkylene alkyl ether (B) described below, the emulsifier contained in the adhesive composition prepared using the obtained polymer solution is used. It is regarded as a polyoxyalkylene alkyl ether (B).

The weight average molecular weight of the acrylic polymer (A) thus obtained is preferably from 50,000 to 2,000,000, preferably from 100,000 to 1,500,000, and more preferably from 300,000 to 1,000,000. When the weight average molecular weight is less than 50,000, the cohesive force of the adhesive composition is small, and there is a tendency that the paste remains after being displaced or peeled off. On the other hand, when the weight average molecular weight exceeds 2,000,000, the fluidity of the polymer is lowered and the wettability tends to be lowered. Further, the weight average molecular weight can be measured by GPC (Gel Permeation Chromatography) and calculated by polystyrene conversion.

(polyoxyalkylene alkyl ether (B))

One or two of the terminal hydroxyl groups of the polyoxyalkylene alkyl ether-based polyoxyalkylene group which may be used in the present invention may form an ether bond with the alkyl group, and may be represented by the following formula (1) or (2). .

R ¹ -O-(R ² O) _n -H (1)

R ¹ -O-(R ² O) _n -R ³ (2)

Here, the general formula (1) is a polyoxyalkylene alkyl ether having an alkyl group R ¹ introduced into a hydroxyl group at one terminal of a polyoxyalkylene group by an ether bond (referred to as a polyoxyalkylene group) The alkyl ether), the general formula (2) is a polyoxyalkylene alkyl ether having an alkyl group R ¹ and R ³ introduced on the hydroxyl group at both ends of the polyoxyalkylene group by an ether bond (referred to as poly Oxyalkylene dialkyl ether).

In the above formulae (1) and (2), R ¹ and R ³ are a C ₁ - C ₂₀ aliphatic hydrocarbon group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a different group. Butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, decyl, isodecyl, undecyl, tridecyl, ten Tetraalkyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl and the like. In the present invention, R ¹ and R ^{3 are} preferably a methyl group, an ethyl group, a butyl group or a 2-ethylhexyl group. Further, in the above formula (2), R ¹ and R ³ may be the same alkyl group or different alkyl groups, and it is preferred that R ¹ is a methyl group and R ³ is a methyl group.

Further, in the above formulae (1) and (2), R ^{2 is} preferably a C ₂ -C ₄ alkylene group, and examples thereof include an exoethyl group (-CH ₂ CH ₂ -) and a stretching propyl group (- CH ₂ CH(CH ₃ )-), butyl (-CH ₂ CH(CH ₂ CH ₃ )-), tetramethylene (-CH ₂ CH ₂ CH ₂ CH ₂ -), and the like. Further, R ² may be an alkylene group or two or more alkylene groups. That is, in the above formulae (1) and (2), (R ² O) _n may be a block copolymer or a random copolymer of two or more kinds of oxygen-extended alkyl groups. In the present invention, R ^{2 is} preferably a propyl group in terms of a lower freezing point (flow point) and a higher lipophilicity (lower surface free energy).

Further, in the above formulae (1) and (2), n represents an addition molar number of the oxygen-extended alkyl group (R ² O) unit. In the present invention, the addition molar number n is preferably from 2 to 22, preferably from 3 to 18. When the molar number n of the oxygen alkyl unit is 2 to 22, the polyoxyalkylene alkyl ether is liquid at a normal use temperature (25 ° C), so that the wettability is good. On the other hand, if the addition number of moles n is less than 2, the boiling point is lowered, and when the adhesive is formed, the organic solvent evaporates and it is difficult to stably exhibit wettability. When the addition number of moles n exceeds 22, The polyoxyalkylene alkyl ether is usually a solid at a general use temperature (25 ° C), and has a low rotational energy of the molecule, so that the wettability is poor.

In the present invention, the polyoxyalkylene alkyl ether has a molecular weight of from 200 to 1,000, preferably from 250 to 950, more preferably from 300 to 900. When the molecular weight is in the range of 200 to 1,000, the polyoxyalkylene alkyl ether is liquid at a normal use temperature (25 ° C), and therefore has good wettability. On the other hand, when the molecular weight is less than 200, the boiling point of the polyoxyalkylene alkyl ether is lowered, and when the adhesive is formed, the organic solvent evaporates and it is difficult to stably exhibit wettability. If the molecular weight exceeds 1,000, the polycondensation is performed. Oxyalkylene alkyl ethers are usually solid at normal use temperatures (25 ° C), and the free energy of rotation of the molecules is lowered, so that the wettability is poor.

Further, in the present invention, the molecular weight of the polyoxyalkylene alkyl ether (B) is derived from the molecular weight of each molecular structure. Further, in the case where a molar amount of the oxygen alkyl group in the commercial product or the like is a mixture of a plurality of kinds, the number average molecular weight is defined as the molecular weight. The number average molecular weight can be measured by GPC (gel permeation chromatography) and calculated by polystyrene conversion.

Specific examples of the polyoxyalkylene alkyl ether which can be used in the present invention include: Polyoxyethylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monobutyl ether, polyoxyethylene mono(2-ethylhexyl) ether, polyoxypropylene monomethyl ether as polyoxyalkylene monoalkyl ether , polyoxypropylene monoethyl ether, polyoxypropylene monobutyl ether, polyoxypropylene mono (2-ethylhexyl) ether, polyoxybutylene monomethyl ether, polyoxybutylene monoethyl ether, polyoxybutylene monobutyl ether, Polyoxybutylene mono(2-ethylhexyl)ether, polyoxytetramethylene monomethyl ether, polyoxytetramethylene monoethyl ether, polyoxytetramethylene monobutyl ether, polyoxytetramethylene single (2-ethylhexyl) ether, etc.; Polyoxyethylene dimethyl ether as polyoxyalkylene dialkyl ether, polyoxyethylene diethyl ether Ether, polyoxyethylene dibutyl ether, polyoxyethylene bis(2-ethylhexyl) ether, polyoxypropylene dimethyl ether, polyoxypropylene diethyl ether, polyoxypropylene dibutyl ether, polyoxypropylene di (2-B) Hexyl)ether, polyoxybutylene dimethyl ether, polyoxybutylene diethyl ether, polyoxybutylene dibutyl ether, polyoxybutylene bis(2-ethylhexyl) ether, polyoxytetramethylene Ether, polyoxytetramethylene diethyl ether, polyoxytetramethylene dibutyl ether, polyoxytetramethylene di(2-ethylhexyl) ether, and the like.

Further, in the present invention, a polyoxyalkylene alkyl ether having two or more oxygen-extended alkyl units can be used. Specific examples of the polyoxyalkylene alkyl alkyl ether having two or more kinds of oxygen-extended alkyl units include polyoxyethylene-polyoxypropylene monoalkyl ether and polyoxyethylene-polyoxypropylene dialkyl. Ether, etc. When the polyoxyalkylene alkyl ether having two or more kinds of oxygen-extended alkyl units is used, the addition molar number n is the total of the addition molar number.

In the present invention, the polyoxyalkylene alkyl ethers may be used singly or in combination.

Specific examples of the polyoxyalkylene alkyl ether to be used in the present invention include the product name "Uniox M-400" manufactured by Nippon Oil Co., Ltd. (polyoxyethylene monomethyl ether having a number average molecular weight of 400), and day. The trade name "Uniox M-550" manufactured by the oil company (polyoxyethylene monomethyl ether with a molecular weight of 500) and the trade name "Uniox MM-550" manufactured by Nippon Oil Co., Ltd. (a polyoxyethylene dimethylene with a molecular weight of 550) Ether); the product name "Smack MP-70" manufactured by Kao Corporation (polyoxypropylene monomethyl ether of 439 molecular weight), and the trade name "Smack MP-40" manufactured by Kao Corporation (polyoxypropylene monomethyl ether of molecular weight 264) The trade name "Leocon 1015H" manufactured by Lion Company (polyoxypropylene mono(2-ethylhexyl) ether with a molecular weight of 800) and the trade name "Leocon 1015B" manufactured by Lion Company (polyoxypropylene monobutyl ether of molecular weight 950) The trade name "Newpol 50HB-260" manufactured by Sanyo Chemical Co., Ltd. (monomethyl ether of polyoxyethylene-polyoxypropylene block polymer with a molecular weight of 880) and the trade name "Newpol 50HB-55" manufactured by Sanyo Chemical Co., Ltd. (Polyoxyethylene-polyoxypropylene embedded in a number average molecular weight of 240) Monomethyl ether of polymer); manufacture of Aoki Oil Industries Co. under the trade name "FINESURF NDB-800" (molecular weight (T.M.W, Theoretical Molecular Weight, theoretical molecular weight) 450 polyoxyethylene-polyoxypropylene block polymer monoterpene ether), manufactured by Aoki Oil & Fats Co., Ltd. under the trade name "FINESURF NDB-1000" (molecular weight (TMW) 550 polyoxyethylene - poly A monoterpene ether of an oxypropylene block polymer, a product name "FINESURF NDB-1400" manufactured by Aoki Oil & Fats Industry Co., Ltd. (a polyoxyethylene-polyoxypropylene block polymer monoterpene ether of a molecular weight (TMW) 700), etc. .

The adhesive composition of the present invention is characterized in that it contains 0.1 part by weight to 100 parts by weight of the polyoxyalkylene alkyl ether (B) having a molecular weight of 200 to 1000, based on 100 parts by weight of the acrylic polymer (A). It is preferably from 0.3 part by weight to 90 parts by weight, more preferably from 0.5 part by weight to 80 parts by weight. When the content of the polyoxyalkylene alkyl ether (B) is in the range of 0.1 part by weight to 100 parts by weight, the wettability of the adhesive can be improved. On the other hand, if the content of the polyoxyalkylene alkyl ether (B) is less than 0.1 part by weight, the ratio of the polyoxyalkylene alkyl ether (B) which may be present on the surface of the adhesive is reduced, and thus becomes It is difficult to obtain the desired wettability, and if it exceeds 100 parts by weight, the viscosity is lowered when the polyoxyalkylene alkyl ether (B) as a liquid is added to the adhesive composition, and the coating property is deteriorated. .

(crosslinking agent (C))

Further, the adhesive composition of the present invention may contain a crosslinking agent (C).

As the crosslinking agent (C) used in the present invention, an isocyanate compound, an epoxy resin, a melamine resin, an aziridine derivative, a metal chelate compound or the like can be used.

As the crosslinking agent (C) in the present invention, an isocyanate crosslinking agent is preferably used from the viewpoint of obtaining a favorable cohesive force by crosslinking by reaction with an acrylic polymer.

The isocyanate-based crosslinking agent used as the crosslinking agent (C) means an isocyanate-regenerating functional group having two or more isocyanate groups in one molecule (including an isocyanate-based functional group temporarily protected by a blocking agent or oligomerization). ) a compound.

Examples of the isocyanate crosslinking agent include aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate; and alicyclic isocyanic acid such as isophorone diisocyanate. An ester; an aliphatic isofluoride ester such as hexamethylene diisocyanate.

More specifically, examples thereof include lower aliphatic polyisocyanates such as butyl diisocyanate and hexamethylene diisocyanate; and lipids such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone diisocyanate; a cyclic isocyanate; an aromatic diisocyanate such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzodimethyl diisocyanate or polymethylene polyphenyl isocyanate; Propane/toluene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry, trade name "Coronate L"), trimethylolpropane / hexamethylene diisocyanate trimer adduct (Nippon Polyurethane Industry Manufactured, trade name "Coronate HL"), isocyanate ester of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry, trade name "Coronate HX"), isocyanate adduct; polyether polyisocyanate, polyester Polyisocyanate and these adducts with various polyols; polyfunctional polyisomers by isocyanurate bond, biuret bond, allophanate bond, etc. Cyanate esters, etc. Among these, an aliphatic isocyanate is preferably used from the viewpoint of reaction rate and wettability.

Further, examples of the epoxy resin include N,N,N',N'-tetraglycidyl metaxylylenediamine and 1,3-bis(N,N-diglycidylaminomethyl). Cyclohexane, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diglycidyl phthalate acrylate, spirodiol diglycidyl ether, etc.; as a melamine-based resin, hexamethylol melamine is exemplified Wait. Examples of the aziridine derivative include a trade name HDI, a trade name TAZM, and a trade name TAZO manufactured by a mutual pharmaceutical company which is a commercially available product. Further, examples of the metal chelate compound include aluminum, iron, tin, titanium, nickel, and the like as a metal component, and examples thereof include acetylene, ethyl acetonate acetate, and ethyl lactate as a chelate component.

The content of the crosslinking agent (C) used in the present invention is preferably from 1 part by weight to 10 parts by weight, more preferably from 2 parts by weight to 6 parts by weight, per 100 parts by weight of the acrylic polymer (A). When the content is less than 1 part by weight, the crosslinking formed by the crosslinking agent becomes unfilled. The tendency of the cohesive force of the adhesive composition to become small. On the other hand, when the content exceeds 10 parts by weight, the cohesive force of the polymer increases, the fluidity decreases, and the wettability tends to be insufficient.

The adhesive composition of the present invention may contain other additives within a range that does not impair the effects thereof, such as an adjustable filler (inorganic filler, organic filler, etc.), an anti-aging agent, an antioxidant, an ultraviolet absorber, and an anti-aging agent. Various additives such as electrostatic agents, lubricants, surfactants, plasticizers, surface lubricants, leveling agents, colorants (pigments, dyes, etc.).

The adhesive layer of the present invention comprises the above-mentioned adhesive composition, and when the adhesive composition contains a crosslinking agent, it is crosslinked. Further, the adhesive sheet of the present invention is formed by forming the adhesive layer on a substrate. At this time, the crosslinking of the adhesive composition is generally performed after the application of the adhesive composition, but the adhesive layer containing the adhesive composition after crosslinking may be transferred onto a support film or the like.

The method of forming the pressure-sensitive adhesive layer can be produced, for example, by applying the above-mentioned pressure-sensitive adhesive composition to a substrate, drying the polymerization solvent or the like, and performing a crosslinking treatment as needed to form an adhesive on the substrate. Method for applying a coating layer; applying the above-mentioned adhesive composition to a release-treated release liner (for example, a polysiloxane-treated release film) or the like, drying a polymerization solvent or the like, and performing a crosslinking treatment as needed A method of forming an adhesive layer and then transferring it onto a substrate. Further, at the time of application of the adhesive composition, one or more solvents other than the polymerization solvent may be newly added as appropriate.

For the substrate, for example, a film made of polyolefin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.), a film made of polyester (polyethylene terephthalate or the like), a film made of a vinyl chloride resin, or a vinyl acetate can be used. Resin film, polyimide resin film, polyamide resin film, fluorine resin film, and cellophane plastic film; Japanese paper, kraft paper, thin cellophane (Glassine) Paper), paper such as Daolin paper, synthetic paper, top coated paper; various fibrous materials (may be any of natural fiber, semi-synthetic fiber or synthetic fiber; for example, cotton fiber, staple fiber, Staple Fiber, Manila hemp, pulp, cockroach, B a cloth such as a woven fabric or a non-woven fabric obtained by separately or blending an acid fiber, a polyester fiber, a polyvinyl alcohol fiber, a polyamide fiber, a polyolefin fiber or the like; a rubber sheet containing natural rubber, butyl rubber or the like A foam sheet comprising a foam such as a foamed polyurethane or a foamed polychloroprene rubber; a metal foil such as an aluminum foil or a copper foil; and a composite of the above. The plastic film may be of an unextended type or an extended type (uniaxially stretched or biaxially stretched).

Further, in order to improve the adhesion between the adhesive layer and the substrate, the surface of the substrate (especially the surface on which the adhesive layer side is provided) may be subjected to, for example, corona discharge treatment, plasma treatment, or primer coating. A known or customary surface treatment such as cloth. The thickness of the substrate can be appropriately selected depending on the purpose, and is usually about 10 μm to 500 μm, preferably about 10 μm to 200 μm.

In the step of applying the adhesive composition of the present invention to the substrate or the release liner in this manner and drying to form an adhesive layer, as a method of drying the adhesive composition, an appropriate method can be appropriately employed depending on the purpose. It is preferred to use a method of heating and drying the above coating film. The heating and drying temperature is preferably from 40 ° C to 200 ° C, more preferably from 50 ° C to 180 ° C, and particularly preferably from 70 ° C to 170 ° C. By setting the heating temperature within the above range, an adhesive layer having excellent adhesive properties can be obtained.

The drying time can be appropriately set to an appropriate time. The drying time is preferably from 5 seconds to 20 minutes, more preferably from 5 seconds to 10 minutes, and particularly preferably from 10 seconds to 5 minutes.

As a method of forming the adhesive layer, various methods can be used. Specific examples thereof include roll coating, contact roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roller coating, bar coating, blade coating, air knife coating, and curtain coating. Coating, lip coating, extrusion coating using a die coater or the like.

The thickness of the adhesive layer is not particularly limited, and is, for example, about 1 μm to 100 μm. It is preferably 2 μm to 50 μm, more preferably 2 μm to 40 μm, and still more preferably 5 μm to 35 μm.

The adhesive sheet of the present invention is provided with the above-mentioned adhesive layer having a high wettability, and is excellent in wettability as compared with the conventional acrylic pressure-sensitive adhesive sheet. Wetting of the adherend can be borrowed The evaluation is carried out by the method described in the following examples, and it is preferred to wet the distance of 100 mm in less than 10 seconds, more preferably 7 seconds or less, further preferably 5 seconds or less. When the wetting time is less than 10 seconds, even if it is bonded to the adherend, it is not particularly pressurized, and it can be sufficiently adhered to the adherend, and bubbles or the like are not substantially mixed.

Further, the adhesive force of the adhesive sheet of the present invention to the acrylic resin sheet or the glass sheet is preferably 0.02 N/250 mm or more, more preferably 0.05 N/250 mm or more, and still more preferably 0.10 N/250 mm or more ( Usually 2.00 N/250 mm or less).

Since the adhesive layer obtained by the present invention is excellent in wettability, it can be used for various adhesive sheets, for example, an adhesive sheet for electrical insulation, an adhesive sheet for double-sided use, an adhesive sheet for surface protection, a masking tape, and a peeling. Type labels and other fields.

Example

Hereinafter, embodiments and the like which specifically show the configuration and effects of the present invention will be described, but the present invention is not limited thereto. Further, the evaluation items in the examples were measured in the following manner.

<Measurement of Weight Average Molecular Weight>

The weight average molecular weight of the produced polymer was measured by GPC (gel permeation chromatography) and calculated by polystyrene conversion.

Device: manufactured by Tosoh, HLC-8220GPC

Pipe column: manufactured by Tosoh, TSKgel Super HZM-H, H-RC, HZ-H

Flow rate: 0.6 ml/min, injection volume: 20 μl, column temperature: 40 °C

Dissolution: THF (tetrahydrofuran, tetrahydrofuran), injection sample concentration: 0.1% by weight

<Evaluation of wettability>

Test piece: 25 mm × 100 mm

Adhered body: glass plate (manufactured by Songlang Glass Industrial Co., Ltd., trade name: "green plate cutting and placing (side grinding)", 100 mm × 100 mm × 1.35 mm)

Number of measurements: 3 times

Measurement environment: (temperature 23 ° C, humidity 50% RH)

(1) Fig. 1 shows a state before bonding of the glass plate of the adherend 1 and the test piece (adhesive sheet) 2 in the measurement of wettability. As shown in Fig. 1, the angle is set to be 20 to 30 in a state in which one of the adhesive layers of the test piece (adhesive sheet) 2 is in contact with the glass plate.

(2) Then, the test piece was released by hand, and only the self-weight was used for lamination, and the time during which the adhesive layer was wetted and spread to the end of the glass plate (distance of 100 mm) was recorded while releasing the hand. The average of the three measurements was taken as the wetting time, and the wetting time was less than 10 seconds.

<Measurement of force>

Each of the prepared adhesive sheets was cut into a size of 250 mm in width and 150 mm in length, and was crimped to a clean waste by immersing in isopropyl alcohol by rolling the 2 kg roller back and forth once. A clean acrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrylite L) and the above-mentioned glass plate were washed 10 times to obtain a sample for adhesion evaluation. The evaluation sample was allowed to stand in a measurement environment of 23° C.×50% RH for 30 minutes, and then the adhesion force was measured using a tensile tester at a tensile speed of 300 mm/min and a peeling angle of 180° [N/250 mm]. .

<Preparation of acrylic polymer (A)>

96 parts by weight of 2-ethylhexyl acrylate (2EHA, 2-ethyl hexyl acrylate) and 4 parts by weight of 2-hydroxy acrylate were added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Ethyl acetate (HEA, 2-hydroxyethyl acrylate), 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator, and 178 parts by weight of ethyl acetate as a solvent, and nitrogen gas was introduced while slowly stirring, and the liquid in the flask was introduced. The polymerization was carried out for about 3 hours while maintaining the temperature at around 60 ° C to prepare an acrylic polymer solution. The obtained acrylic polymer (A) had a weight average molecular weight of 420,000.

<Preparation of acrylic polymer (B)>

With stirring blade, thermometer, nitrogen inlet tube, condenser and dropping funnel 96 parts by weight of 2-ethylhexyl acrylate (2EHA), 4 parts by weight of 2-hydroxyethyl acrylate (HEA), 3 parts by weight of acrylic acid (AA, acrylic acid), 0.2 parts by weight as a polymerization starter were added to the four-necked flask. An azobisisobutyronitrile and 183 parts by weight of ethyl acetate as a solvent were introduced while introducing nitrogen gas while slowly stirring, and the liquid temperature in the flask was maintained at around 60 ° C for about 3 hours to prepare an acrylic polymerization. Solution. The obtained acrylic polymer (B) had a weight average molecular weight of 420,000.

<Preparation of acrylic polymer (C)>

96 parts by weight of 2-ethylhexyl acrylate (2EHA) and 4 parts by weight of 2-hydroxyethyl acrylate (HEA) were added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel. 4 parts by weight of N-vinyl-2-pyrrolidone (NVP, N-vinyl-2-pyrrolidone), 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator, and 185 parts by weight of acetic acid B as a solvent The ester was introduced while introducing nitrogen gas while slowly stirring, and the temperature of the liquid in the flask was maintained at around 60 ° C for about 3 hours to prepare an acrylic polymer solution. The obtained acrylic polymer (C) had a weight average molecular weight of 420,000.

<Preparation of acrylic polymer (D)>

96 parts by weight of 2-ethylhexyl acrylate (2EHA) and 4 parts by weight of 2-hydroxyethyl acrylate (HEA) were added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel. 3 parts by weight of methyl methacrylate (MMA), 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator, and 183 parts by weight of ethyl acetate as a solvent, and nitrogen gas was introduced while slowly stirring. The liquid temperature in the flask was maintained at around 60 ° C for about 3 hours to prepare an acrylic polymer solution. The obtained acrylic polymer (D) had a weight average molecular weight of 420,000.

<Preparation of acrylic polymer (E)>

31 parts by weight of 2-ethylhexyl acrylate (2EHA) and 4 parts by weight of 2-hydroxyethyl acrylate (HEA) were added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel. 65 parts by weight of EA, ethyl acrylate, 0.2 weight The amount of azobisisobutyronitrile as a polymerization initiator and 178 parts by weight of ethyl acetate as a solvent were introduced, and nitrogen gas was introduced while slowly stirring, and the temperature in the flask was maintained at around 60 ° C to carry out polymerization for about 3 hours. The reaction was carried out to prepare an acrylic polymer solution. The obtained acrylic polymer (E) had a weight average molecular weight of 420,000.

Example 1

Using 100 parts by weight of the above-mentioned acrylic polymer (A) (solid content), 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name "Smack MP-70"), and 4 parts by weight were added as Cross-isocyanuric acid hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry, trade name "Coronate HX") and 0.015 parts by weight of dioctyltin dilaurate as a catalyst (Tokyo Fine Chemicals) (Tokyo Fine Chemical Co., Ltd., trade name "OL-1"), and further diluted with toluene so that the solid content concentration is 29% by weight, and then stirred to obtain an adhesive composition solution.

The above adhesive composition solution was applied to "Lumirror S10" manufactured by Toray Co., Ltd. as a polyethylene terephthalate film (PET) having a thickness of 38 μm, and was removed by drying at 130 ° C for 30 seconds. The solvent forms an adhesive layer (thickness 20 μm). Thereafter, it was covered with a surface-treated release film by a release agent, and cured at 50 ° C for 1 day to obtain an adhesive sheet.

Example 2

An adhesive sheet was obtained in the same manner as in Example 1 except that the amount of the polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name "Smack MP-70") was 10 parts by weight.

Example 3

An adhesive sheet was obtained in the same manner as in Example 1 except that the amount of the polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name "Smack MP-70") was 50 parts by weight.

Example 4

An adhesive sheet was obtained in the same manner as in Example 1 except that the amount of the polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name "Smack MP-70") was 75 parts by weight. .

Example 5

75 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 264 (manufactured by Kao Corporation, trade name "Smack MP-40") was added in place of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name "Smack MP" In addition to the above, an adhesive sheet was obtained in the same manner as in Example 1.

Example 6

1 part by weight of polyoxypropylene monomethyl ether having a molecular weight of 264 (manufactured by Kao Corporation, trade name "Smack MP-40") was added in place of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name "Smack MP" In addition to the above, an adhesive sheet was obtained in the same manner as in Example 1.

Example 7

25 parts by weight of a polyoxypropylene mono(2-ethylhexyl)ether having a molecular weight of 800 (manufactured by Lion Co., Ltd., trade name "Leocon 1015H") was added in place of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation). An adhesive sheet was obtained in the same manner as in Example 1 except for the name "Smack MP-70".

Example 8

25 parts by weight of a polyoxyethylene monomethyl ether of a number average molecular weight of 400 (manufactured by NOF Corporation, trade name "Uniox M-400") was used instead of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name) An adhesive sheet was obtained in the same manner as in Example 1 except for "Smack MP-70".

Example 9

Formulating 25 parts by weight of polyoxyethylene-polyoxypropylene block polymerization of a number average molecular weight of 880 The monomethyl ether (manufactured by Sanyo Chemical Co., Ltd., trade name "Newpol 50HB-260") was used instead of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name "Smack MP-70"). An adhesive sheet was obtained in the same manner as in Example 1 except for the same.

Example 10

10 parts by weight of a polyoxyethylene dimethyl ether having a number average molecular weight of 880 and a number average molecular weight of 550 (manufactured by NOF Corporation, trade name "Uniox MM-550") instead of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (King) An adhesive sheet was obtained in the same manner as in Example 1 except that the product was manufactured by the company, trade name "Smack MP-70".

Example 11

4 parts by weight of a trimethylolpropane/toluene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry, trade name "Coronate L") was added in place of 4 parts by weight of hexamethylene diisocyanate as a crosslinking agent. An adhesive sheet was obtained in the same manner as in Example 1 except that a cyanurate body (C/HX) (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HX") was used.

Example 12

An adhesive sheet was obtained in the same manner as in Example 1 except that 100 parts by weight (solid content) acrylic polymer (B) was blended in place of 100 parts by weight (solid content) of the acrylic polymer (A).

Example 13

An adhesive sheet was obtained in the same manner as in Example 1 except that 100 parts by weight (solid content) acrylic polymer (C) was blended in place of 100 parts by weight (solid content) of the acrylic polymer (A).

Example 14

In the same manner as in Example 1, except that 100 parts by weight (solid content) acrylic polymer (D) was blended in place of 100 parts by weight (solid content) of the acrylic polymer (A). Obtained an adhesive sheet.

Example 15

An adhesive sheet was obtained in the same manner as in Example 1 except that 100 parts by weight (solid content) acrylic polymer (E) was blended in place of 100 parts by weight (solid content) of the acrylic polymer (A).

Comparative example 1

1 part by weight of polyoxypropylene (manufactured by Sanyo Chemical Co., Ltd., trade name "Sannix PP-400") having a number average molecular weight of 400 at both ends and having a hydroxyl group at the same time, and 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, An adhesive sheet was obtained in the same manner as in Example 1 except for the trade name "Smack MP-70".

Comparative example 2

10 parts by weight of polyoxypropylene (manufactured by Sanyo Chemical Co., Ltd., trade name "Sannix PP-2000") having a number average molecular weight of 2,000 and having a hydroxyl group at both ends was replaced by 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, An adhesive sheet was obtained in the same manner as in Example 1 except for the trade name "Smack MP-70".

Comparative example 3

1 part by weight of polyoxypropylene monobutyl ether having a molecular weight of 1900 (manufactured by Aoki Oil & Fats Co., Ltd., trade name "BLAUNON BUP-1900") was added in place of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name " An adhesive sheet was obtained in the same manner as in Example 1 except for Smack MP-70").

Comparative example 4

1 part by weight of a polyoxypropylene monoalkyl ether having a molecular weight of 3,300 (manufactured by Asahi Glass Co., Ltd., trade name "PREMNOL S 1004F") was added in place of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name "Smack MP" In addition to the above, an adhesive sheet was obtained in the same manner as in Example 1.

Comparative Example 5

25 parts by weight of a polyoxypropylene monoalkyl ether having a molecular weight of 5,000 (manufactured by Asahi Glass Co., Ltd., trade name "PREMNOL S 1005") was added in place of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation, trade name "Smack MP" In addition to the above, an adhesive sheet was obtained in the same manner as in Example 1.

Comparative Example 6

3 parts by weight of phenoxy polyethylene glycol polypropylene glycol monomethacrylate (manufactured by NOF, trade name "Blemmer 43PAPE-600B") having a molecular weight of 775 was added in place of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 ( An adhesive sheet was obtained in the same manner as in Example 1 except that the product name "Smack MP-70" was manufactured by Kao Corporation.

Comparative Example 7

25 parts by weight of polyoxyethylene (manufactured by Sanyo Chemical Co., Ltd., trade name "PEG-400") having a number average molecular weight of 400, which is a hydroxyl group at both ends, in place of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation) An adhesive sheet was obtained in the same manner as in Example 1 except for the name "Smack MP-70".

Comparative Example 8

10 parts by weight of polyoxyethylene (manufactured by Sanyo Chemical Co., Ltd., trade name "PEG-2000") having a number average molecular weight of 2,000 and a hydroxyl group at the both ends was replaced by 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439 (manufactured by Kao Corporation). An adhesive sheet was obtained in the same manner as in Example 1 except for the name "Smack MP-70".

Comparative Example 9

25 parts by weight of a mono(2-ethylhexyl)ether of a polyoxyethylene-polyoxypropylene block polymer having a molecular weight of 1400 (manufactured by Lion Company, trade name "Leocon 1020H") was used instead of 25 parts by weight of polyoxypropylene having a molecular weight of 439. An adhesive sheet was obtained in the same manner as in Example 1 except that monomethyl ether (manufactured by Kao Corporation, trade name "Smack MP-70") was used.

The adhesive sheets produced in the examples and the comparative examples were evaluated for wettability and adhesion by the above-described evaluation method. The results are shown in Tables 1 and 2.

In the above Tables 1 to 2, the abbreviations of the additives and the crosslinking agents indicate the following commercial products.

. MP-70: The brand name "Smack MP-70" manufactured by Kao Corporation (polyoxypropylene monomethyl ether of 439 molecular weight)

. MP-40: The brand name "Smack MP-40" manufactured by Kao Corporation (polyoxypropylene monomethyl ether of molecular weight 264)

. 1015H: The trade name "Leocon 1015H" manufactured by Lion Company (polyoxypropylene mono(2-ethylhexyl) ether with a molecular weight of 800)

. M-400: The brand name "Uniox M-400" manufactured by Nippon Oil Co., Ltd. (polyoxyethylene monomethyl ether with a molecular weight of 400)

. 50HB-260: The trade name "Newpol 50HB-260" manufactured by Sanyo Chemical Co., Ltd. (monomethyl ether of polyoxyethylene-polyoxypropylene block polymer with a number average molecular weight of 880)

. MM-500: The trade name "Uniox MM-550" manufactured by Nippon Oil Co., Ltd. (a polyoxyethylene dimethyl ether with a molecular weight of 550)

. PP-400: Sanken Chemical Company's trade name "Sannix PP-400" (Polyoxypropylene with a number average molecular weight of 400: hydroxyl at both ends)

. PP-2000: Sanken Chemical Company's trade name "Sannix PP-2000" (Polyoxypropylene with a number average molecular weight of 2000: hydroxyl at both ends)

. BUP-1900: The brand name "BLAUNON BUP-1900" manufactured by Aoki Oil & Fats Industry Co., Ltd. (molecular weight (T.M.W) 1900 polyoxypropylene monobutyl ether)

. 1004F: The brand name "PREMNOL S 1004F" manufactured by Asahi Glass Co., Ltd. (polyoxypropylene monoalkyl ether with a molecular weight of 3,300)

. 1005: The brand name "PREMNOL S 1005" manufactured by Asahi Glass Co., Ltd. (polyoxypropylene monoalkyl ether having a molecular weight of 5000)

. 43PAPE: The trade name "Blemmer 43PAPE-600B" manufactured by Nippon Oil Co., Ltd. (phenolic polyethylene glycol polypropylene glycol monomethacrylate with a molecular weight of 775)

. PEG-400: trade name "PEG-400" manufactured by Sanyo Chemical Co., Ltd. (polyoxyethylene with a molecular weight of 400: hydroxyl at both ends)

. PEG-2000: Trade name "PEG-2000" manufactured by Sanyo Chemical Co., Ltd. (Polyoxyethylene with a number average molecular weight of 2000: hydroxyl at both ends)

. 1020H: trade name "Leocon 1020H" manufactured by Lion Company (single (2-ethylhexyl) ether of polyoxyethylene-polyoxypropylene block polymer having a molecular weight of 1400)

. C/HX: trade name "Coronate HX" manufactured by Nippon Polyurethane Industry Co., Ltd. (isocyanurate body of hexamethylene diisocyanate)

. C/L: trade name "Coronate L" manufactured by Nippon Polyurethane Industry (trimethylolpropane/toluene diisocyanate trimer adduct)

From the above results, it was confirmed that an adhesive composition containing 0.1 to 100 parts by weight of a polyoxyalkylene alkyl ether (B) having a molecular weight of 200 to 1000 with respect to 100 parts by weight of the acrylic polymer (A) to (E) is used. The adhesive sheet of the embodiment of the article can obtain good wettability.

On the other hand, it was confirmed that the end of the additive prepared as the polyoxyalkylene alkyl ether (B) in Comparative Examples 1, 2, 7, and 8 was not an alkyl ether but a hydroxyl group, and the wettability was inferior. Further, in Comparative Examples 2, 3, 4, 5, 8, and 9, the polyoxyalkylene alkyl ether (B) had a molecular weight of more than 1,000 and was inferior in wettability. Further, in the comparative example 6, the end of the additive to be added as the polyoxyalkylene alkyl ether (B) was not an alkyl ether but a phenyl group (aromatic substituent), and the wettability was poor.

1‧‧‧adhesive body

2‧‧‧Test piece (adhesive sheet)

Claims (8)

An adhesive composition comprising an acrylic polymer (A) and a polyoxyalkylene alkyl ether (B) having a molecular weight of 200 to 1000, and the content of the polyoxyalkylene alkyl ether (B) is relatively The acrylic polymer (A) is used in an amount of from 0.1 part by weight to 100 parts by weight per 100 parts by weight. The adhesive composition of claim 1, wherein the polyoxyalkylene alkyl ether (B) is a polyoxypropylene alkyl ether. The adhesive composition of claim 1, wherein the alkyl group constituting the above polyoxyalkylene alkyl ether (B) is a methyl group, an ethyl group, a butyl group or a 2-ethylhexyl group. The adhesive composition according to claim 1, wherein the acrylic polymer (A) is at least 80% by weight to 99.9% by weight of an alkyl (meth)acrylate having an alkyl group having 4 to 18 carbon atoms and 0.1. The functional group-containing monomer in a weight % to 20% by weight is obtained as a monomer component. The adhesive composition of claim 1, which contains 1 part by weight to 10 parts by weight of the crosslinking agent (C) based on 100 parts by weight of the acrylic polymer (A). The adhesive composition of claim 5, wherein the crosslinking agent (C) is an isocyanate crosslinking agent. An adhesive layer comprising the adhesive composition of claim 1. An adhesive sheet formed by forming an adhesive layer of claim 7 on a substrate.