KR20130097112A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer and pressure-sensitive adhesive sheet - Google Patents

Abstract

PURPOSE: An adhesive composition is provided to have an excellent wettability, and to be able to provide an adhesive sheet capable of preventing the generation of bubbles as the adhesion to a substance to be adhered is excellent without separate pressurization. CONSTITUTION: An adhesive composition includes (A) acrylic polymer (B) polyoxyalkylene alkyl ether with the molecular weight of 200-1000. The content of (B) polyoxyalkylene alkyl ether is 0.1-100.0 parts by weight to 100.0 parts by weight of (A) acrylic polymer. (B) polyoxyalkylene alkyl ether is polyoxypropylene alkyl ether. (A) acrylic polymer includes 80-99.9 weight% of alkyl (meth)acrylate having at least C4-18 alkyl and 0.1-20 weight% of functional group-containing monomer as a monomer component. [Reference numerals] (AA) Test piece (adhesion sheet); (BB) Body to be adhered

Description

PRESSURE-SENSITIVE ADHESIVE COMPOSITION, PRESSURE-SENSITIVE ADHESIVE LAYER AND PRESSURE-SENSITIVE ADHESIVE SHEET}

This invention relates to the adhesive sheet excellent in wettability, the adhesive layer used for this, and an adhesive composition.

The pressure-sensitive adhesive sheet has a gel-like soft pressure-sensitive adhesive layer on a substrate such as a plastic film or paper, and the pressure-sensitive adhesive layer exhibits adhesive strength by being wet to the adherend while being solid. In other words, the pressure-sensitive adhesive layer is required to be sufficiently wet with respect to the adherend. On the other hand, the adhesive layer needs cohesion force (hardness) to the extent which resists peeling. Therefore, an adhesive sheet is designed in consideration of wettability and cohesion force as opposing characteristics.

For this reason, in general, an adhesive sheet is pressurized when bonding to a to-be-adhered body, and in some cases, it is pressurized in a heated state, and it is constructed so that it may fully adhere to a to-be-adhered body. Thus, when pressurization and heating are possible at the time of construction, even if the wettability of an adhesive tape is inferior, it can be used, but when a to-be-adhered body is a micro part or a problem arises about heating, such construction is difficult. Become.

Moreover, as a case where wettability with respect to a to-be-adhered body becomes a problem, the case where a bubble enters between an to-be-adhered body and an adhesive sheet can be considered. For example, in order to prevent a bubble from remaining when bonding a decorative film, it is known to form a convex protrusion in an adhesive layer, or to form a concave stripe, and to push out a bubble, but these are essentially wettability of an adhesive sheet. It is not to improve.

As a method of improving the wettability of an adhesive sheet, it is known to make the acryl-type polymer which comprises an adhesive layer into the graft polymer structure which has an alkylene oxide in a side chain. That is, in patent document 1, 51-100 weight% of (meth) acrylic-acid alkylene oxide adducts, 0-49 weight% of (meth) acrylic-type monomers other than the above, and 0-49 weight% of other polymerizable monomers are monomers. The surface protection film formed by forming the adhesive layer which crosslinks the (meth) acrylic-type (co) polymer used as a component and the adhesive composition containing a crosslinking agent on a support film is disclosed. In addition, the crosslinking agent is mix | blended and used for patent document 2, As a solvent-type re-peelable adhesive composition containing an adhesive polymer, this adhesive polymer has a polymer structure whose glass transition temperature is 0 degreeC or more, and a C4-C12 alkyl group. A long chain portion containing monomer (B) and a functional group containing monomer (C) containing an alkyl (meth) acrylate (A), an alkylene oxide chain and / or a long chain alkyl group as essential components, and other monomers ( A pressure-sensitive adhesive layer obtained from a solvent-based re-peelable pressure-sensitive adhesive composition, which is a graft and / or block polymer having a polymer structure synthesized from a raw material monomer component containing D), wherein the pressure-sensitive adhesive layer is formed on at least one side of the support base material. An adhesive product for peeling is disclosed.

However, in invention of patent document 2, even if it is the adhesive surface property of a narrow range of 4 cm x 4 cm, 20 seconds or more are required until the whole is soaked, and it did not have sufficient wettability.

Japanese Patent Laid-Open No. 2005-200540 Japanese Patent Publication No. 2009-227737

Therefore, the objective of this invention is providing the adhesive composition excellent in wettability, an adhesive layer, and the adhesive sheet using the same in order to solve the problem with the conventional acrylic adhesive.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, this inventor contains the acrylic polymer and the polyoxyalkylene alkyl ether of the molecular weight 200-1000, and content of the said polyoxyalkylene alkyl ether is 100 weight of the said acrylic polymer. With the adhesive sheet which forms the adhesive layer which consists of an adhesive composition which is 0.1 weight part-100 weight part with respect to a base material, it turned out that the said subject can be solved and came to solve this invention.

That is, the reason which can improve the wettability of an adhesive in this invention is by mix | blending specific amount of polyoxyalkylene alkyl ether whose molecular weight is 200-1000. It is thought that compounding polyoxyalkylene alkyl ether in the present invention contributes to the improvement of wettability due to the low rotational energy of the ether bonds and the low polarity of the end groups. If both ends are polyoxyalkylene of the hydroxyl group, sufficient improvement in wettability is not achieved because it is because the surface free energy of the hydroxyl group is high. Moreover, in this invention, it is necessary to be the structure which the alkyl group couple | bonded with at least one terminal of polyoxyalkylene. This should not be, for example, an aromatic substituent (phenyl group or methylphenyl group). The reason for this is considered that the aromatic substituent has a high steric hindrance, so that the degree of freedom of rotation of the molecules is lowered. Moreover, the molecular weight of polyoxyalkylene alkyl ether needs to be 200-1000. If the molecular weight is too large, the freezing point (flow point) is increased, so the degree of freedom of rotation of the molecule is lowered, which makes it difficult to improve the wettability.

The present invention contains an acrylic polymer (A) and a polyoxyalkylene alkyl ether (B) having a molecular weight of 200 to 1000, wherein the content of the polyoxyalkylene alkyl ether (B) is 100 parts by weight of the acrylic polymer (A). It provides 0.1 to 100 parts by weight with respect to the pressure-sensitive adhesive composition.

Especially in the adhesive composition of this invention, it is preferable that the said polyoxyalkylene alkyl ether (B) is polyoxypropylene alkyl ether. Moreover, it is preferable that the alkyl group which comprises the said polyoxyalkylene alkyl ether (B) is a methyl group, an ethyl group, a butyl group, or 2-ethylhexyl group.

Furthermore, this invention consists of 80 weight%-99.9 weight% of alkyl (meth) acrylates which have an alkyl group of 4-18 carbon atoms, and 0.1 weight%-20 weight% of functional group containing monomers as a monomer component the said acrylic polymer (A) at least. It provides the pressure-sensitive adhesive composition, characterized in that.

The present invention also provides the pressure-sensitive adhesive composition comprising 1 to 10 parts by weight of the crosslinking agent (C) based on 100 parts by weight of the acrylic polymer (A). It is preferable that especially the said crosslinking agent (C) is an isocyanate type crosslinking agent.

Moreover, this invention provides the adhesive layer which forms the adhesive layer which consists of the said adhesive composition, and this adhesive layer on a base material.

The adhesive composition, the adhesive layer, and the adhesive sheet of this invention are excellent in wettability compared with the conventional acrylic adhesive sheet. For this reason, the adhesive sheet of this invention can fully adhere to a to-be-adhered body, even if it does not pressurize especially when bonding to an to-be-adhered body, and can fully prevent generation | occurrence | production of an air bubble etc .. Therefore, it can use as various adhesive sheets.

1 is a schematic view for explaining a method of evaluating wettability in an example.

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

The adhesive composition of this invention contains 0.1 weight part-100 weight part of polyoxyalkylene alkyl ethers (B) whose molecular weight is 200-1000 with respect to 100 weight part of 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 usually used in an adhesive composition can be used. As such an acrylic polymer (A), since it is easy to balance adhesiveness, cohesion, and other adhesive characteristics, at least 80 weight%-99.9 weight% of alkyl (meth) acrylate which has a C4-C18 alkyl group, and a functional group containing monomer It is preferable to contain 0.1 to 20 weight% as a monomer component.

As a specific example of the alkyl (meth) acrylate which has a C4-C18 alkyl group which comprises an acryl-type polymer (A), butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acryl Latex, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) Acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, Uryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl ( Meth) acrylic And the like can be mentioned alkyl (meth) acrylate and the like. These may be used independently and may use 2 or more types together.

It is preferable that it is 80 weight%-99.9 weight% in all the monomer components, and, as for the content rate of the alkyl (meth) acrylate which has a C4-C18 alkyl group, it is more preferable that it is 90 weight%-99 weight%.

The functional group-containing monomer constituting the acrylic polymer (A) imparts polarity and reactivity to the acrylic polymer, or contributes to the formation of a crosslinked structure by reacting with a crosslinking agent described later, for example, containing functional groups such as carboxyl groups and hydroxyl groups. A functional group containing monomer can be mentioned.

As a specific example of a functional group containing monomer, Carboxyl group containing monomers, such as (meth) acrylic acid, itaconic acid, maleic acid, a fumaric acid, a crotonic acid;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates such as [4- (hydroxymethyl) cyclohexyl] methyl acrylate; .

Moreover, in this invention, as a functional group containing monomer, N-methylol acrylamide, N-methylol methacrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, N- (2-hydroxypropyl) acrylamide, N- (2-hydroxypropyl) methacrylamide, N- (1-hydroxypropyl) acrylamide, N- (1-hydroxypropyl) methacrylamide, N- (3-hydroxypropyl) acrylamide, N- (3-hydroxypropyl) methacrylamide, N- (2-hydroxybutyl) acrylamide, N- (2-hydroxybutyl) methacrylamide, N- (3-hydroxybutyl) acrylamide, N- (3-hydroxybutyl) methacrylamide, N- (4-hydroxybutyl) acrylamide, N- (4-hydroxybutyl) methacrylamide, etc. N-hydroxyalkyl (meth) acrylamide of;

Monomers having an epoxy group such as glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, allyl glycidyl ether,

(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N- Monomers having amide groups such as methylol propane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-vinylcarboxylic acid amide;

Monomers having amino groups such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate and t-butylaminoethyl (meth) acrylate;

Monomers having cyano groups such as acrylonitrile and methacrylonitrile;

Monomers having keto groups such as diacetone (meth) acrylamide, diacetone (meth) acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetoacetate, and vinyl acetoacetate;

Isocyanate group-containing monomers such as 2- (meth) acryloyloxyethyl isocyanate; . These functional group containing monomers may be used independently and may be used in combination.

It is preferable that it is 0.1 weight%-20 weight% in all the monomer components, and, as for content of a functional group containing monomer, it is more preferable that it is 1 weight%-10 weight%. If the content of the functional group-containing monomer is less than 0.1% by weight, the addition effect thereof becomes difficult to be obtained, for example, crosslinking formation becomes insufficient, cohesive force of the pressure-sensitive adhesive composition cannot be obtained, and the pressure-sensitive adhesive sheet shifts or adheres at the time of fixing the article. When the sheet is peeled off, a paste residue may occur. On the other hand, when the content rate of a functional group containing monomer exceeds 20 weight%, since the cohesion force of an acryl-type polymer becomes large, fluidity | liquidity may fall and wettability may fall.

In the present invention, the monomer component constituting the acrylic polymer (A) is, in addition, a copolymerizable monomer for adjusting the glass transition point and the adhesion of the acrylic polymer (A) in a range that does not impair the effects of the present invention. Can be used. As such a copolymerizable monomer, the alkyl (meth) acrylate which has alkyl groups of less than 4 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate, etc. Ryu;

Vinyl esters such as vinyl acetate and vinyl propionate;

Aromatic vinyl compounds such as styrene, substituted styrene (α-methylstyrene, etc.) and vinyltoluene;

Alicyclic hydrocarbon (meth) acrylates such as cyclohexyl (meth) acrylate, cyclopentyldi (meth) acrylate, and isobornyl (meth) acrylate;

Aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate and benzyl (meth) acrylate;

Olefin monomers such as ethylene, propylene, isoprene, butadiene and isobutylene;

Halogen atom-containing monomers such as vinyl chloride and vinylidene chloride;

Alkoxy group-containing monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate;

Vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether;

N-vinyl-2-pyrrolidone, N- (1-methylvinyl) pyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N- (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate Monomers having heterocycles such as; And the like.

In this invention, you may use as a copolymerizable monomer the monomer which has several functional groups in 1 molecule individually or in combination of 2 or more types as appropriate. Such a polyfunctional monomer can be useful for improving heat resistance and cohesiveness of the pressure-sensitive adhesive. Specific examples of the polyfunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and (poly Mono or polyalkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and (poly) propylene glycol di (meth) acrylate; Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, tetramethylol methane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, etc. are mentioned.

As a copolymerizable monomer, you may use the monomer which has an alkoxysilyl group individually or in combination of 2 or more types as appropriate. Such an alkoxysilyl group-containing monomer can be helpful for improving heat resistance and cohesiveness of the pressure-sensitive adhesive. As a specific example of the alkoxy silyl group containing monomer, 3- (meth) acryloxypropyl trimethoxysilane, 3- (meth) acryloxypropyl triethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, And (meth) acryloxyalkylsilane derivatives such as 3- (meth) acryloxypropylmethyldiethoxysilane and vinyltrimethoxysilane.

These copolymerizable monomers can be used individually or in combination of 2 or more types as appropriate. For example, a copolymerizable monomer can be used in the range of 20 weight% or less (0 weight%-20 weight%) among all monomer components, and is usually 15 weight% or less (0 weight%-15 weight%), It is preferable to set it as 10 weight% or less (0 weight%-10 weight%). The minimum of the usage-amount in the case of using a copolymerizable monomer is not specifically limited, What is necessary is just the quantity which can achieve the objective of using the said monomer. Usually, it is suitable to make the usage-amount of a copolymerizable monomer into 0.001 weight% or more in all the monomer components.

The acrylic polymer (A) used for this invention can be manufactured by superposing | polymerizing the said monomer component by well-known polymerization methods, such as solution polymerization, block polymerization, emulsion polymerization, and various radical polymerization. Moreover, any of a random copolymer, a block copolymer, a graft copolymer, etc. may be sufficient as the acryl-type polymer obtained.

In solution polymerization, for example, ethyl acetate, toluene or the like is used as the polymerization solvent. You may mix and use these polymerization solvents. As a specific solution polymerization example, reaction is performed under reaction conditions of 2 hours or more (for example, about 5 hours to 30 hours) at 50 degreeC-about 70 degreeC by adding a polymerization initiator under inert gas streams, such as nitrogen.

The polymerization initiator, chain transfer agent, emulsifier, etc. used for radical polymerization are not specifically limited, It can select suitably and can use. In addition, the weight average molecular weight of the acryl-type polymer mentioned later can be controlled with the usage-amount of a polymerization initiator, a chain transfer agent, and reaction conditions, and the usage-amount is adjusted suitably according to these types.

As a polymerization initiator, for example, 2,2'- azobisisobutyronitrile, 2,2'- azobis (2-amidinopropane) dihydrochloride, 2,2'- azobis [2- (5 -Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) sulfate, 2,2'-azobis (N, N'- Azo initiators such as dimethylene isobutyl amidine) and 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057); Persulfates such as potassium sulfate and ammonium persulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxy Neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, di (4-methylbenzoyl) peroxy Peroxide initiators such as dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-hexylperoxy) cyclohexane, t-butylhydroperoxide, hydrogen peroxide, persulfate and sodium hydrogen sulfite Although a redox initiator which combined peroxide and a reducing agent, such as a combination, a combination of a peroxide, and sodium ascorbate, etc. are mentioned, It is not limited to this.

Although the said polymerization initiator may be used independently and may be used in mixture of 2 or more type, It is preferable that content as a whole is 0.005 weight part-about 1 weight part with respect to 100 weight part of all monomer components, 0.02 weight part It is more preferable that it is about 0.5 weight part.

As a chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, thioglucolic acid 2-ethylhexyl, 2,3-dimercapto-1 Propanol etc. are mentioned. Although a chain transfer agent may be used independently and may mix and use 2 or more types, content as a whole is about 0.1 weight part or less with respect to 100 weight part of all monomer components.

Moreover, as an emulsifier used when emulsion-polymerizing, anionic emulsifiers, such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, polyoxyethylene alkyl ether ammonium sulfate, and polyoxyethylene alkyl phenyl ether sodium sulfate, for example And nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer. These emulsifiers may be used independently and may use 2 or more types together.

Moreover, as a reactive emulsifier, the emulsifier into which radically polymerizable functional groups, such as a propenyl group and an allyl ether group, were introduce | transduced is mentioned. Specifically, for example, aqualon HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (all are manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), Adeka Riasorb SE10N (ADEKA) Company) etc. are mentioned. Since a reactive emulsifier is accommodated in a polymer chain after superposition | polymerization, water resistance becomes good and it is preferable. As for the usage-amount of an emulsifier, 0.5 weight part-1 weight part are more preferable from a 0.3 weight part-5 weight part, and superposition | polymerization stability and mechanical stability with respect to 100 weight part of monomer components. In addition, when superposing | polymerizing using the emulsifier corresponding to the polyoxyalkylene alkyl ether (B) mentioned later, the said emulsifier contained in the adhesive composition manufactured using the polymer solution obtained is polyoxyalkylene alkyl ether (B). Is considered.

The acrylic polymer (A) thus obtained has a weight average molecular weight of 50,000 to 2 million, preferably 100,000 to 1.5 million, more preferably 300,000 to 1 million. When the weight average molecular weight is less than 50,000, the cohesion force of the pressure-sensitive adhesive composition decreases, so that a deviation occurs at the time of adhesion fixing, or a pool residue occurs at the time of peeling. On the other hand, when the weight average molecular weight exceeds 2 million, the fluidity | liquidity of a polymer falls and there exists a tendency for wettability to fall. In addition, a weight average molecular weight can be measured by GPC (gel permeation chromatography) and it can calculate by polystyrene conversion.

(Polyoxyalkylene Alkyl Ether (B))

The polyoxyalkylene alkyl ether which can be used by this invention is a compound in which one or both of the terminal hydroxyl groups of polyoxyalkylene form an ether group with an alkyl, and can be represented as following General formula (1) or (2). .

R ¹ -O- (R ² O) _n -H (1)

R ¹ -O- (R ² O) _n -R ³ (2)

Formula (1) is polyoxyalkylene alkyl ether (called polyoxyalkylene monoalkyl ether) which introduce | transduced the alkyl group R <^1> by ether bond to the hydroxyl group of one terminal of polyoxyalkylene here, General formula (2) is Polyoxyalkylene alkyl ether (called polyoxyalkylenedialkyl ether) which introduce | transduced the alkyl groups R <^1> and R <^3> by ether bond to the hydroxyl group of both terminals of polyoxyalkylene.

In the above formulas (1) and (2), R ¹ and R ³ are C ₁ to C ₂₀ aliphatic hydrocarbon groups, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, isodecyl group, undecyl group, tridecyl group, tetradecyl group, pentadecyl group , Hexadecyl group, heptadecyl group, octadecyl group, eicosyl group 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. In addition, in the said General formula (2), although R <^1> and R <^3> may be the same alkyl group or a different alkyl group, Preferably R <^1> is a methyl group and R <^3> is a methyl group.

In the above formulas (1) and (2), R ² is preferably an alkylene group of C ₂ to C ₄ , for example, an ethylene group (-CH ₂ CH _2- ), a propylene group (-CH ₂ CH ( CH ₃ )-), butylene group (-CH ₂ CH (CH ₂ CH ₃ )-), tetramethylene group (-CH ₂ CH ₂ CH ₂ CH _2- ) and the like. R ² may be one kind of alkylene group or two or more kinds of alkylene groups. That is, in the general formulas (1) and (2), (R ² O) _n may be a block copolymer or a random copolymer of two or more oxyalkylene groups. In the present invention, R ² is particularly preferably a propylene group in terms of low solidification point (flow point) and high lipophilicity (low surface free energy).

In General Formulas (1) and (2), n represents the added mole number of the oxyalkylene (R ² O) unit. In the present invention, the added mole number n is 2 to 22, preferably 3 to 18. If the added mole number n of the oxyalkylene unit is 2 to 22, since the polyoxyalkylene alkyl ether is a liquid at a general use temperature (25 ° C), there is an advantage in that wettability is good. On the other hand, when the added mole number n is less than 2, the boiling point is lowered, and it may be difficult to evaporate with the organic solvent at the time of adhesive formation, and to stably express wettability. When the added mole number n exceeds 22, polyoxyalkylene alkyl ether In general use temperature (25 degreeC), since it is a solid normally and the freedom degree of rotation of a molecule | numerator falls, wettability may be inferior.

In the present invention, the molecular weight of the polyoxyalkylene alkyl ether is 200 to 1000, preferably 250 to 950, more preferably 300 to 900. If the molecular weight is in the range of 200 to 1000, the polyoxyalkylene alkyl ether is a liquid at a general use temperature (25 ° C), and therefore, there is an advantage of good wettability. On the other hand, when the molecular weight is less than 200, the polyoxyalkylene alkyl ether may have a lower boiling point, evaporate with the organic solvent when the pressure-sensitive adhesive is formed, and it may be difficult to stably express wettability. When the molecular weight exceeds 1000, polyoxyalkyl Lenalkyl ethers are usually solid at a general use temperature (25 ° C), and the wettability may be inferior because the degree of freedom of rotation of the molecules decreases.

In addition, in this invention, the molecular weight of polyoxyalkylene alkyl ether (B) is molecular weight derived from individual molecular structure. In addition, when it is a mixture of what has the added mole number of oxyalkylene in a commercial item etc., let number average molecular weight be its own molecular weight. The number average molecular weight can be measured by GPC (gel permeation chromatography), and can be calculated by polystyrene conversion.

As a specific example of the polyoxyalkylene alkyl ether which can be used by this invention,

As polyoxyalkylene monoalkyl ether, polyoxyethylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monobutyl ether, polyoxyethylene mono 2-ethylhexyl ether, polyoxypropylene monomethyl 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 mono 2-ethylhexyl ether and the like;

As polyoxyalkylenedialkyl ether, polyoxyethylene dimethyl ether, polyoxyethylene diethyl ether, polyoxyethylene dibutyl ether, polyoxyethylene di 2-ethylhexyl ether, polyoxypropylene dimethyl ether, polyoxypropylene diethyl ether , Polyoxypropylene dibutyl ether, polyoxypropylene di 2-ethylhexyl ether, polyoxybutylene dimethyl ether, polyoxybutylene diethyl ether, polyoxybutylene dibutyl ether, polyoxybutylenedi 2-ethylhexyl ether, poly Oxytetramethylene dimethyl ether, polyoxytetramethylene diethyl ether, polyoxytetramethylene dibutyl ether, polyoxytetramethylene di 2-ethylhexyl ether and the like.

In addition, in this invention, polyoxyalkylene alkyl ether which has 2 or more types of oxyalkylene units can be used. As a specific example of the polyoxyalkylene alkyl ether which has 2 or more types of oxyalkylene units, polyoxyethylene polyoxypropylene monoalkyl ether, polyoxyethylene polyoxypropylene dialkyl ether, etc. are mentioned, for example. . The addition mole number n at the time of using the polyoxyalkylene alkyl ether which has 2 or more types of oxyalkylene units makes the sum total its addition mole number.

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

As a specific example of the polyoxyalkylene alkyl ether which can be used by this invention, the brand name "Uniox M-400" (polyoxyethylene monomethyl ether of the number average molecular weight 400) by Nichiyu Corporation, the "uniox M- 550 "(polyoxyethylene monomethyl ether having a number average molecular weight of 500) and copper" Uniox MM-550 "(polyoxyethylene dimethyl ether having a number average molecular weight of 550); Brand name "Smack MP-70" (polyoxypropylene monomethyl ether having a molecular weight of 439) manufactured by Kao Corporation, and "Smack MP-40" (polyoxypropylene monomethyl ether having a molecular weight of 264); Lion Co., Ltd. brand name "Leocon 1015H" (polyoxypropylene mono 2-ethylhexyl ether having a molecular weight of 800), and "Leocon 1015B" (polyoxypropylene monobutyl ether having a molecular weight of 950); Sanyo Chemical Co., Ltd. brand name "Newpole 50HB-260" (monomethyl ether of polyoxyethylene-polyoxypropylene block polymer of number average molecular weight 880), same "Newpole 50HB-55" (polyoxyethylene- of number average molecular weight 240) Monomethyl ether of polyoxypropylene block polymer); Polyoxyethylene having the trade name "FINESURF NDB-800" (monodecyl ether of a polyoxyethylene-polyoxypropylene block polymer having a molecular weight (TMW) 450) manufactured by Aoki Yuji Co., Ltd. Monodecylether of ethylene-polyoxypropylene block polymer), the same "FINESURF NDB-1400" (monodecylether of polyoxyethylene-polyoxypropylene block polymer having a molecular weight (TMW) 700); And the like.

In the adhesive composition of this invention, 0.1 weight part-100 weight part of polyoxyalkylene alkyl ethers (B) whose molecular weight is 200-1000 are contained with respect to 100 weight part of acrylic polymer (A), Preferably, 0.3 to 90 parts by weight, more preferably 0.5 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 pressure-sensitive 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 proportion of the polyoxyalkylene alkyl ether (B) which may be present on the pressure-sensitive adhesive is reduced, making it difficult to obtain the desired wettability, and 100 weight When the amount is exceeded, the viscosity decreases when the polyoxyalkylene alkyl ether (B), which is a liquid, is placed in the pressure-sensitive adhesive composition, resulting in poor coatability.

(Cross-linking system (C))

In addition, the adhesive composition of this invention may contain the crosslinking agent (C).

As a crosslinking agent (C) used for this invention, an isocyanate compound, an epoxy resin, a melamine resin, an aziridine derivative, a metal chelate compound, etc. are used.

As a crosslinking agent (C) in this invention, it is preferable to use an isocyanate type crosslinking agent from a viewpoint of obtaining appropriate cohesion force by crosslinking formation in reaction with an acrylic polymer.

An isocyanate type crosslinking agent used as a crosslinking agent (C) means the compound which has two or more isocyanate groups (including the isocyanate regeneration type functional group which temporarily protected the isocyanate group by blocking agent or water quantification, etc.) in 1 molecule.

As an isocyanate type crosslinking agent, aromatic isocyanate, such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanate, such as isophorone diisocyanate, aliphatic isocyanate, such as hexamethylene diisocyanate, etc. are mentioned.

More specifically, Lower aliphatic polyisocyanates, such as butylene diisocyanate and hexamethylene diisocyanate, cycloaliphatic diisocyanates, such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, 2, 4-, for example Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Co., Ltd., Coronate L), trimethylolpropane / hexamethylene diisocyanate trimer adduct (Nippon Polyurethane Co., Ltd., brand name coronate HL), isocyanurate body of Nippon Polyurethane Co., Ltd., brand name Coro Nate H Isocyanate adducts such as X), polyether polyisocyanates, polyester polyisocyanates, and polyisocyanates polyfunctionalized with adducts of these and various polyols, isocyanurate bonds, biuret bonds, allophanate bonds, and the like. Can be. Among them, it is preferable to use aliphatic isocyanate from the viewpoint of reaction rate and wettability.

As the epoxy resin, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and ethylene glycol di Hexamethylol melamine etc. are mentioned as melamine type resins, such as glycidyl ether, propylene glycol diglycidyl ether, terephthalic acid diglycidyl ester acrylate, and spiroglycol diglycidyl ether. As an aziridine derivative, the Sogo Pharmaceutical Co., Ltd. make, a brand name HDU, a brand name TAZM, a brand name TAZO etc. as a commercial item are mentioned, for example. Moreover, as a metal chelating compound, aluminum, iron, tin, titanium, nickel, etc. are mentioned as a metal component, acetylene, methyl acetoacetate, ethyl lactate, etc. are mentioned as a chelate component.

It is preferable that it is 1 weight part-10 weight part with respect to 100 weight part of acrylic polymer (A), and, as for content of a crosslinking agent (C) used for this invention, it is more preferable that it is 2 weight part-6 weight part. When content is less than 1 weight part, crosslinking formation by a crosslinking agent becomes inadequate and there exists a tendency for the cohesion force of an adhesive composition to become small. On the other hand, when content exceeds 10 weight part, the cohesion force of a polymer is large and fluidity falls and there exists a tendency for wettability to become inadequate.

The pressure-sensitive adhesive composition of the present invention may contain other additives as long as it does not impair the effect thereof. For example, fillers (inorganic fillers, organic fillers, etc.), anti-aging agents, antioxidants, ultraviolet absorbers, charging Various additives, such as an inhibitor, a lubricating agent, surfactant, a plasticizer, a surface lubricant, a leveling agent, and a coloring agent (pigment, dye, etc.) may be mix | blended.

The adhesive layer of this invention comprises the said adhesive composition, and when a crosslinking agent is contained in an adhesive composition, it is made by crosslinking. Moreover, the adhesive sheet of this invention forms such an adhesive layer on a base material. In that case, although crosslinking of an adhesive composition is generally performed after application | coating of an adhesive composition, it is also possible to transfer the adhesive layer which consists of an adhesive composition after crosslinking to a support film etc.

As a method of forming an adhesive layer, the adhesive composition is apply | coated to a base material, the polymerization solvent etc. are dried and removed, and a crosslinking process is formed as needed, and the said adhesive composition is formed, for example. It is apply | coated to the peeling liner (for example, the release film which carried out the silicone process) etc. which carried out the peeling process, dry-removed a polymerization solvent, etc., crosslinking-processes as needed, and formed by the method of transferring to a base material after forming an adhesive layer. In addition, in application | coating of an adhesive composition, you may add a 1 or more types of solvent other than a polymerization solvent suitably.

The base material may be, for example, a film made of polyolefin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.), a film made of polyester (polyethylene terephthalate, etc.), a vinyl chloride resin film, a vinyl acetate resin film, or poly Plastic films such as a mid resin film, a polyamide resin film, a fluorine resin film, and other cellophanes; Papers such as Japanese paper, kraft paper, glassine paper, fine paper, synthetic paper, and top coated paper; Various fibrous materials (natural fibers, semi-synthetic fibers or synthetic fibers may be used. For example, cotton fibers, stable fibers, manila hemp, pulp, rayon, acetate fibers, polyester fibers, polyvinyl alcohol fibers, polyamides). Fibers such as woven fabrics and nonwoven fabrics of single fibers or blends of fibers, polyolefin fibers and the like; Rubber sheets made of natural rubber, butyl rubber and the like; Foam sheets composed of foams such as foamed polyurethane and foamed polychloroprene rubber; Metal foils such as aluminum foil and copper foil; These complexes; Etc. may be used. The plastic film may be a non-stretched type or a stretched type (uniaxially stretched type or biaxially stretched type).

In addition, in order to improve the adhesiveness between the pressure-sensitive adhesive layer and the base material, the surface of the base material (in particular, the surface of the side where the pressure-sensitive adhesive layer is provided) may be, for example, known such as corona discharge treatment, plasma treatment, application of a primer, or the like. Ordinary surface treatment may be performed. Although the thickness of a base material can be suitably selected according to the objective, Generally, it is about 10 micrometers-500 micrometers, Preferably it is about 10 micrometers-200 micrometers.

Thus, in the process of apply | coating and drying the adhesive composition of this invention on a base material or a peeling liner, and forming an adhesive layer, the method suitable for drying an adhesive composition can be employ | adopted according to the objective. Preferably, the method of heat-drying the said coating film is used. The heat drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and particularly preferably 70 ° C to 170 ° C. By setting the heating temperature in the above range, a pressure-sensitive adhesive layer having excellent adhesive properties can be obtained.

As the drying time, an appropriate time may be employed. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

Various methods are used as a formation method of an adhesive layer. Specifically, for example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brush, spray coating, deep roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, die coater, etc. And extrusion coating methods.

The thickness of an adhesive layer is not specifically limited, For example, it is about 1 micrometer-100 micrometers. Preferably they are 2 micrometers-50 micrometers, More preferably, they are 2 micrometers-40 micrometers, More preferably, they are 5 micrometers-35 micrometers.

The adhesive sheet of this invention provides the adhesive layer with high wettability mentioned above, and is excellent in wettability compared with the conventional acrylic adhesive sheet. The wettability to the adherend can be evaluated by the method described in Examples described later, and it is preferable to wet the distance of 100 mm in a time of less than 10 seconds, more preferably 7 seconds or less, even more preferably 5 seconds or less. All. When wet time is less than 10 second, even when it does not pressurize especially when joining to a to-be-adhered body, it fully adheres to an to-be-adhered body and does not generate | occur | produce foam etc. substantially.

Moreover, it is preferable that the adhesive force of the adhesive sheet of this invention is 0.02 N / 250 mm or more to an acryl plate or a glass plate, More preferably, it is 0.05 N / 250 mm or more, More preferably, it is 0.10 N / 250 mm or more (usually 2.00 N / 250 mm or less).

Since the adhesive layer obtained is excellent in wettability, it is useful in the field of various adhesive sheets, for example, the adhesive sheet for electrical insulation, the adhesive sheet for both surfaces, the adhesive sheet for surface protection, the masking tape, a repeelable label, etc. Do.

[Example]

EMBODIMENT OF THE INVENTION Hereinafter, although the Example etc. which show a structure and effect of this invention concretely are demonstrated, this invention is not limited to this. In addition, the evaluation item in the Example etc. was measured as follows.

<Measurement of weight average molecular weight>

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

Apparatus: manufactured by Tosoh Corporation, HLC-8220 GPC

Column: Tosoh Corporation, TSKgel Super HZM-H, H-RC, HZ-H

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

Eluent: THF, injection sample concentration: 0.1% by weight

<Evaluation of wettability>

Test piece: 25 mm × 100 mm

Substrate: Glass plate (manufactured by Matsunami Glass Industrial Co., Ltd., product name: blue plate cut-off product (edge polishing) 100mm × 100mm × 1.35mm)

3 measurements

Measuring environment: (temperature 23 ℃, humidity 50% RH)

(1) In FIG. 1, the state before bonding of a glass plate and a test piece in the measurement of wettability is shown. As shown in FIG. 1, the angle was 20 degrees-30 degrees in the state which contacted the glass plate a part of adhesive layer surface of a test piece (adhesive sheet).

(2) Next, the test piece was removed from the test piece, bonded only by its own weight, and the time when the adhesive layer was wetted to the end of the glass plate (distance of 100 mm) was recorded at the same time as the hand was released. The average value measured 3 times was made into the wet time, and the wet time was made into the pass less than 10 second.

<Measurement of adhesive force>

Each produced adhesive sheet was cut into a size of 250 mm in width and 150 mm in length, and the clean acrylic plate (Mitsubishi Rayon Co., Ltd. make, brand name: Acrylite L), which was cut and rubbed and washed with 10 rounds of clean water infiltrated with isopropyl alcohol, was used. The 2 kg roller was rolled on the glass plate and crimped | bonded by the method of 1 round-trip, and it was set as the sample for adhesive force evaluation. After leaving this evaluation sample for 30 minutes in 23 degreeC x 50% RH measurement environment, the adhesive force [N / 250mm] was measured on the conditions of 300 mm / min of tensile velocity and 180 degree of peel angles using the tensile tester.

<Production of Acrylic Polymer (A)>

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

<Production of Acrylic Polymer (B)>

96 parts by weight of 2-ethylhexyl acrylate (2EHA), 4 parts by weight of 2-hydroxyethyl acrylate (HEA), and acrylic acid in a four-necked flask equipped with a stirring vane, a thermometer, a nitrogen gas introduction tube, a cooler, and a dropping funnel. AA) 3 parts by weight, 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator, 183 parts by weight of ethyl acetate as a solvent were introduced, nitrogen gas was introduced while stirring slowly, and the liquid temperature in the flask was kept at around 60 ° C. The polymerization reaction was carried out for 3 hours to prepare an acrylic polymer solution. The weight average molecular weight of the obtained acrylic polymer (B) was 420,000.

<Production of Acrylic Polymer (C)>

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

<Production of Acrylic Polymer (D)>

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

<Production of Acrylic Polymer (E)>

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

Example 1

Using 100 parts by weight of the acrylic polymer (A) (solid content), 25 parts by weight of polyoxypropylene monomethyl ether (manufactured by Kao Corporation, trade name "Smack MP-70") having a molecular weight of 439 and a hexamethylene diisocyanate 4 parts by weight of isocyanurate (Nippon Polyurethane Co., Ltd., brand name "coronate HX"), 0.015 part by weight of dioctyl tin dilaurate (Tokyo Fine Chemicals, brand name "OL-1"), Furthermore, after diluting with toluene so that solid content concentration might be 29 weight%, it stirred and obtained the adhesive composition solution.

Applying the pressure-sensitive adhesive composition solution on a "Lumir S10" manufactured by Toray Industries Co., Ltd., a polyethylene terephthalate (PET) film having a thickness of 38 μm, and drying the solvent at 130 ° C. for 30 seconds to remove the solvent to form an adhesive layer (thickness 20 μm). Formed. Then, it covered with the release film surface-treated with the mold release agent, cured at 50 degreeC for 1 day, and obtained the adhesive sheet.

Example 2

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

Example 3

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

Example 4

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

Example 5

Polyoxypropylene monomethyl ether having a molecular weight of 439 (trade name "Smack MP-40" with a molecular weight of 264) instead of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439. Except having mix | blended 75 weight part, it carried out similarly to Example 1, and obtained the adhesive sheet.

Example 6

Polyoxypropylene monomethyl ether having a molecular weight of 439 (trade name "Smack MP-40" with a molecular weight of 264) instead of 25 parts by weight of polyoxypropylene monomethyl ether having a molecular weight of 439. Except having mix | blended 1 weight part, it carried out similarly to Example 1, and obtained the adhesive sheet.

Example 7

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"), polyoxypropylene mono 2-ethylhexyl ether having a molecular weight of 800 (manufactured by Lion Corporation, trade name "Leocon 1015H Except having mix | blended 25 weight part "), it carried out similarly to Example 1, and obtained the adhesive sheet.

Example 8

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"), polyoxyethylene monomethyl ether having a number average molecular weight of 400 (manufactured by Nichiyu Corporation, trade name "Uniox M-" The adhesive sheet was obtained like Example 1 except having mix | blended 25 weight part of 400 ").

Example 9

Monomethyl ether of polyoxyethylene-polyoxypropylene block polymer having a number average molecular weight of 880 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"). Except having mix | blended 25 weight part of manufacture and brand name "Newpole 50HB-260", it carried out similarly to Example 1, and obtained the adhesive sheet.

Example 10

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"), polyoxyethylene dimethyl ether having a number average molecular weight of 880 and having a number average molecular weight of 550 (manufactured by Nichiyu Corporation, trade name " Except having mix | blended 10 weight part of uniox MM-550 "), it carried out similarly to Example 1, and obtained the adhesive sheet.

Example 11

Trimethylolpropane / tolylene diisocyanate trimer adduct (Nippon) instead of 4 parts by weight of isocyanurate (C / HX) (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate HX") of hexamethylene diisocyanate as a crosslinking agent. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, except that 4 parts by weight of the polyurethane industry company make and brand name "coronate L") were blended.

Example 12

The adhesive sheet was obtained like Example 1 except having mix | blended 100 weight part (solid content) of the acrylic polymer (B) instead of 100 weight part (solid content) of an acrylic polymer (A).

Example 13

The adhesive sheet was obtained like Example 1 except having mix | blended 100 weight part (solid content) of acrylic polymer (C) instead of 100 weight part (solid content) of an acrylic polymer (A).

Example 14

The adhesive sheet was obtained like Example 1 except having mix | blended 100 weight part (solid content) of acrylic polymer (D) instead of 100 weight part (solid content) of an acrylic polymer (A).

Example 15

The adhesive sheet was obtained like Example 1 except having mix | blended 100 weight part (solid content) of acrylic polymer (E) instead of 100 weight part (solid content) of an acrylic polymer (A).

Comparative Example 1

Instead of 25 parts by weight of polyoxypropylene monomethyl ether (manufactured by Kao Corporation, trade name "Smack MP-70") having a molecular weight of 439, polyoxypropylene (manufactured by Sanyo Chemical Co., Ltd. Except having mix | blended 1 weight part of Knicks PP-400 "), it carried out similarly to Example 1, and obtained the adhesive sheet.

Comparative Example 2

Instead of 25 parts by weight of polyoxypropylene monomethyl ether (manufactured by Kao Corporation, trade name "Smack MP-70") having a molecular weight of 439, polyoxypropylene (manufactured by Sanyo Chemical Co., Ltd. Except having mix | blended 10 weight part of Knicks PP-2000 "), it carried out similarly to Example 1, and obtained the adhesive sheet.

Comparative Example 3

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"), polyoxypropylene monobutyl ether having a molecular weight of 1900 (manufactured by Aoki Holding Co., Ltd., product name "BLAUNON BUP-1900" ), And an adhesive sheet was obtained in the same manner as in Example 1 except that 1 part by weight of) was added.

Comparative Example 4

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"), polyoxypropylene monoalkyl ether having a molecular weight of 3300 (manufactured by Asahi Glass, trade name "PREMNOL S 1004F") Except having mix | blended 1 weight part, it carried out similarly to Example 1, and obtained the adhesive sheet.

Comparative Example 5

Polyoxypropylene monoalkyl ether having a molecular weight of 5000 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") (manufactured by Asahi Glass, trade name "PREMNOL S 1005") Except having mix | blended 25 weight part, it carried out similarly to Example 1, and obtained the adhesive sheet.

Comparative Example 6

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"), a phenoxy polyethylene glycol polypropylene glycol monomethacrylate having a molecular weight of 775 (manufactured by Nichiyu Corporation, trade name "B Except having mix | blended 3 weight part of Remmer 43PAPE-600B "), it carried out similarly to Example 1, and obtained the adhesive sheet.

Comparative Example 7

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

Comparative Example 8

Instead of 25 parts by weight of polyoxypropylene monomethyl ether (manufactured by Kao Corporation, trade name "Smack MP-70") having a molecular weight of 439, polyoxyethylene (manufactured by Sanyo Chemical Co., Ltd., product name "PEG) having a number average molecular weight of 2000 at which both ends are hydroxyl groups. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, except that 10 parts by weight of -2000 ") was blended.

Comparative Example 9

Mono 2-ethylhexyl ether of the polyoxyethylene-polyoxypropylene block polymer of 1,400 molecular weight instead of 25 weight part of polyoxypropylene monomethyl ether (the Kao Corporation make, brand name "Smack MP-70") of molecular weight 439 (Lion company) Except having mix | blended 25 weight part of manufacture and brand name "Leocon 1020H", it carried out similarly to Example 1, and obtained the adhesive sheet.

About the adhesive sheet produced by the Example and the comparative example, wettability and adhesiveness were evaluated by the said evaluation method. The results are shown in Table 1 and Table 2.

In the said Table 1-Table 2, the symbol of an additive and a crosslinking agent represents the following commercial items.

MP-70: Trade name "Smack MP-70" manufactured by KAO Corporation (polyoxypropylene monomethyl ether having a molecular weight of 439)

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

1015H: The brand name "Leocon 1015H" (polyoxypropylene mono 2-ethylhexyl ether having a molecular weight of 800) manufactured by Lion Corporation,

M-400: Nichiyu Corporation make " Uniox M-400 " (polyoxyethylene monomethyl ether having a number average molecular weight of 400)

50HB-260: Brand name "Newpole 50HB-260" by Sanyo Chemical Co., Ltd. (monomethyl ether of polyoxyethylene-polyoxypropylene block polymer having a number average molecular weight of 880)

MM-500: Nichiyu Co., Ltd. brand name "Uniox MM-550" (polyoxyethylene dimethyl ether having a number average molecular weight of 550)

PP-400: Sanyo Chemical Co., Ltd. make " Sannix PP-400 " (polyoxypropylene having a number average molecular weight of 400: hydroxyl groups at both ends)

PP-2000: Sanyo Chemical Co., Ltd. brand name "Sannix PP-2000" (polyoxypropylene having a number average molecular weight of 2000: both ends are hydroxyl groups)

BUP-1900: Brand name "BLAUNON BUP-1900" (polyoxypropylene monobutyl ether having a molecular weight (T.M.W) 1900), manufactured by Aoki Yuji Co., Ltd .;

1004F: The brand name "PREMNOL S 1004F" by the Asahi Glass Co., Ltd. (polyoxypropylene monoalkyl ether having a molecular weight of 3300)

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

43PAPE: Nichiyu Corporation make " Bremer 43PAPE-600B " (phenoxypolyethylene glycol polypropylene glycol monomethacrylate having a molecular weight of 775)

PEG-400: Sanyo Chemical Co., Ltd. brand name "PEG-400" (polyoxyethylene having a number average molecular weight of 400: hydroxyl groups at both ends)

PEG-2000: Brand name "PEG-2000" by Sanyo Chemical Co., Ltd. (polyoxyethylene having a number average molecular weight of 2000: both terminals are hydroxyl groups)

1020H: Lion product name "Leocon 1020H" (mono 2-ethylhexyl ether of polyoxyethylene-polyoxypropylene block polymer having a molecular weight of 1400)

C / HX: Nippon Polyurethane Co., Ltd. brand name "coronate HX" (isocyanurate of hexamethylene diisocyanate)

C / L: Nippon Polyurethane Co., Ltd. brand name "coronate L" (trimethylolpropane / tolylene diisocyanate trimer adduct)

From the above result, the adhesive sheet of the Example which uses the adhesive composition containing 0.1-100 weight part of polyoxyalkylene alkyl ethers (B) whose molecular weight is 200-1000 with respect to 100 weight part of acrylic polymers (A)-(E). In it, it was confirmed that favorable wettability is obtained.

On the other hand, in Comparative Examples 1, 2, 7, and 8, the terminal of the additive to be blended as the polyoxyalkylene alkyl ether (B) is not an alkyl ether but a hydroxyl group, and wettability is inferior. In Comparative Examples 2, 3, 4, 5, 8, and 9, the molecular weight of the polyoxyalkylene alkyl ether (B) exceeds 1000, and the wettability is inferior. Moreover, in the comparative example 6, it was confirmed that the terminal of the additive mix | blended as polyoxyalkylene alkyl ether (B) is not an alkyl ether but a phenyl group (aromatic substituent), and it is inferior to wettability.

Claims (8)

It contains an acrylic polymer (A) and the polyoxyalkylene alkyl ether (B) whose molecular weight is 200-1000,
The adhesive composition whose content of the said polyoxyalkylene alkyl ether (B) is 0.1 weight part-100 weight part with respect to 100 weight part of said acrylic polymers (A). The method of claim 1,
The said polyoxyalkylene alkyl ether (B) is polyoxypropylene alkyl ether, The adhesive composition characterized by the above-mentioned. The method of claim 1,
The pressure-sensitive adhesive composition, wherein the alkyl group constituting the polyoxyalkylene alkyl ether (B) is a methyl group, an ethyl group, a butyl group or a 2-ethylhexyl group. The method of claim 1,
The acrylic polymer (A) comprises 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% to 20% by weight of a functional group-containing monomer as monomer components. Pressure-sensitive adhesive composition. The method of claim 1,
1 to 10 parts by weight of the crosslinking agent (C) is contained based on 100 parts by weight of the acrylic polymer (A). The method of claim 5,
The said crosslinking agent (C) is an isocyanate type crosslinking agent, The adhesive composition characterized by the above-mentioned. The pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition of claim 1. The adhesive sheet which forms the adhesive layer of Claim 7 on a base material.

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