KR20190077022A - Resin composition for pressure-sensitive adhesive and pressure-sensitive adhesive sheet - Google Patents

Abstract

상기 비닐 단량체 (b)가 알킬기의 탄소수가 8 이상인 알킬(메트)아크릴레이트 (b1)을 포함하고, 상기 (메트)아크릴계 공중합체 (A)의 소각 X선 산란 측정으로 측정한 1차 피크의 반값폭 X가 하기 식 (i)을 만족시킨다.
0<X≤0.12 …(i)
(식 중, R¹은 수소 원자, 메틸기 또는 CH₂OH를 나타내고, R²는 OR³, 할로겐 원자, COR⁴, COOR⁵, CN, CONR⁶R⁷, NHCOR⁸ 또는 R⁹를 나타내고, Q는 2 이상의 구성 단위 (a')를 포함하는 주쇄 부분을 나타내고, Z는 말단기를 나타낸다.)Provided are a resin composition for a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet which can form a pressure-sensitive adhesive layer having a sufficient holding power and an appropriate range of adhesive force and a low substrate stain resistance due to residual adhesive. (Meth) acrylic copolymer (A) having a constituent unit derived from a macromonomer (a) and a constituent unit derived from a vinyl monomer (b), wherein the macromonomer (a) (a ') and at least two structural units represented by the following formula (1)

Wherein the vinyl monomer (b) comprises an alkyl (meth) acrylate (b1) having an alkyl group having a carbon number of 8 or more, and the half-value of the first peak measured by the incinerating X-ray scattering measurement of the (meth) The width X satisfies the following formula (i).
0 < (i)
(Wherein, R ¹ is a hydrogen atom, a methyl group or CH ₂ OH, R ² is OR ^3, halogen, COR ^4, COOR ^5, CN, CONR ⁶ R ^7, NHCOR represents an ⁸ or R ^9, Q is Represents a main chain portion containing two or more structural units (a '), and Z represents a terminal group.

Description

Resin composition for pressure-sensitive adhesive and pressure-sensitive adhesive sheet

The present invention relates to a resin composition for a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet.

The present application claims priority based on Japanese Patent Application No. 2016-235193, filed on December 2, 2016, the contents of which are incorporated herein by reference.

Conventionally, a wide variety of copolymers having different physical properties have been synthesized by polymerizing a vinyl monomer alone or copolymerizing two or more vinyl monomers. In general, a homopolymer of a vinyl monomer can not cope with various physical properties requirements, and thus a method of copolymerizing two or more vinyl monomers or mixing two or more kinds of polymers has been used. However, when two or more vinyl monomers are simply copolymerized, the characteristics of each vinyl monomer unit tend to be averaged. Moreover, merely mixing two or more kinds of polymers often does not sufficiently mix the polymers, and the properties of each vinyl monomer unit are often impaired.

To solve such problems, a copolymer using a macromonomer has been studied. For example, in the field of point-stick adhesives, the following have been proposed as compositions using such copolymers.

(1) An adhesive composition comprising a copolymer dispersed in an aqueous medium having a specific solid content by copolymerizing an ethylenically unsaturated monomer with a macromonomer having a number average molecular weight of 2,000 g / mole to 50,000 g / mole (Patent Document 1) .

(2) A resin composition for a pressure-sensitive adhesive obtained by copolymerizing an alkyl (meth) acrylate monomer and a macromonomer having a number average molecular weight of 1,000 to 200,000 and a glass transition temperature of 30 to 150 ° C.

International Publication No. 2002/022755 Japanese Patent Laid-Open No. 11-158450

However, in the copolymers described in Patent Documents 1 and 2, it is difficult to maintain the adhesive force in an appropriate range while increasing the holding power and lowering the stain resistance of the substrate. For example, when the adhesive layer adhered to the substrate is peeled off from the substrate after the adhesive tape has been peeled off from the substrate in a high temperature environment or after a long period of time has elapsed, substrate contamination due to adhesive residue remaining on the adhesive surface is likely to occur . In addition, when the cohesive force of the copolymer is increased, the viscosity at the time of coating the pressure-sensitive adhesive as a blend increases, and coating unevenness tends to occur. Therefore, it is necessary to increase low molecular weight components such as diluting solvents and diluting monomers, Or the control of the adhesive property becomes difficult.

It is an object of the present invention to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet capable of forming a pressure-sensitive adhesive layer having a sufficient holding power and an appropriate range of adhesive force and having low stain resistance to substrates due to residual pressure- .

The present invention has the following aspects.

[1] A resin composition for a point adhesive comprising a macromonomer (a) and a (meth) acrylic copolymer (A) having a constituent unit derived from a macromonomer (a) and a constituent unit derived from a vinyl monomer (A ') represented by the following formula (1), and at least two structural units represented by the following formula

Wherein the vinyl monomer (b) comprises an alkyl (meth) acrylate (b1) having an alkyl group having a carbon number of 8 or more, and the half-value of the first peak measured by the incinerating X-ray scattering measurement of the (meth) And the width X satisfies the following formula (i).

0 &lt; (i)

(Wherein R ¹ represents a hydrogen atom, a methyl group or CH ₂ OH, and R ² represents OR ³ , a halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ , NHCOR ⁸ or R ⁹ ,

R ³ to R ⁸ are each independently a hydrogen atom, an alkyl group having an unsubstituted or substituted group, an alicyclic group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, a heteroaryl having an unsubstituted or substituted group A nonaromatic heterocyclic group having an unsubstituted or substituted group, an aralkyl group having an unsubstituted or substituted group, an alkaryl group having an unsubstituted or substituted group, an organosilyl group having an unsubstituted or substituted group, (Poly) organosiloxane group having a substituted or substituted group, and the substituents in these groups are each an alkyl group, an aryl group, a heteroaryl group, a nonaromatic heterocyclic group, an aralkyl group, an alkaryl group, a carboxylic acid group, An acid ester group, an epoxy group, a hydroxyl group, an alkoxy group, a primary amino group, a secondary amino group, a tertiary amino group, an isocyanato group, a sulfonic acid group and a halogen atom Is at least one member selected from the group, R ⁹ represents an aryl group, or unsubstituted or heteroaryl group having a substituent ring, or unsubstituted heterocyclic group of the non-aromatic group having a ring or a substituent having or substituted unsubstituted , The substituents in these groups are each an alkyl group, an aryl group, a heteroaryl group, a nonaromatic heterocyclic group, an aralkyl group, an alkaryl group, a carboxylic acid group, a carboxylic acid ester group, an epoxy group, a hydroxy group, , A secondary amino group, a tertiary amino group, an isocyanato group, a sulfonic acid group, an alkyl group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, an olefin group having an unsubstituted or substituted group and a halogen atom . &Lt; / RTI &gt; R represents a hydrogen atom, an alkyl group having an unsubstituted or substituted group, an alicyclic group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, a heteroaryl group having an unsubstituted or substituted group, , An unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, an unsubstituted or substituted organosilyl group, or an unsubstituted or substituted aralkyl group having an unsubstituted or substituted Poly) organosiloxane group, Q represents a main chain portion containing two or more structural units (a '), and Z represents a terminal group.

[2] The resin composition for a pressure-sensitive adhesive according to [1], wherein the (meth) acrylic copolymer (A) has a weight average molecular weight of 1,000 to 1,000,000.

[3] The resin composition for a pressure-sensitive adhesive according to [1] or [2], wherein the content of the structural unit derived from the macromonomer (a) is 3 to 60 mass% with respect to the total mass of the total structural units.

[4] The resin composition for a pressure-sensitive adhesive according to any one of [1] to [3], wherein the macromonomer (a) has a number average molecular weight of 100 or more and 100,000 or less.

[5] The resin composition for a pressure-sensitive adhesive according to any one of [1] to [4], wherein the (meth) acrylic copolymer (A) satisfies the condition of the formula (ii).

0.1? X / Y? (ii)

(X represents the half-width of the first-order peak measured by the incineration X-ray scattering measurement and the peak position Y of the one-dimensional scattering profile)

[6] The resin composition for a pressure-sensitive adhesive according to any one of [1] to [5], wherein the polymer TgB obtained by polymerizing Tga of the macromonomer (a) and the vinyl monomer (b) satisfies the relationship of the formula (4).

Tga-TgB> 0 ℃ ... (4)

[7] Any one of [1] to [6], wherein the solubility parameter 隆 a of the constituent unit derived from the macromonomer (a) and the solubility parameter 隆 b of the constituent unit derived from the vinyl monomer (b) Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;

δa-δb> 0 ... (5)

[8] The resin composition for a pressure-sensitive adhesive as described in any one of [1] to [7], wherein the solution viscosity when the (meth) acrylic copolymer (A) is made into a 50% acetic acid ethyl solution is 10 to 800,000 mPa · s .

[9] A pressure-sensitive adhesive sheet using the resin composition for a pressure-sensitive adhesive according to any one of [1] to [8].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet which can form a pressure-sensitive adhesive layer having a sufficient holding power and an appropriate range of adhesive force and a low substrate stain resistance due to residual pressure-sensitive adhesive. Further, according to the copolymer of the present invention, the viscosity of the formulation at the time of coating can be set in an appropriate range.

The following definitions apply throughout this specification and claims.

"Vinyl monomer" means a monomer having an ethylenically unsaturated bond (polymerizable carbon-carbon double bond).

The "(meth) acrylic copolymer" means a copolymer in which at least a part of the constituent unit is a constituent unit derived from a (meth) acrylic monomer. The (meth) acryl-based polymer may further contain a constituent unit derived from a monomer other than the (meth) acrylic monomer (for example, styrene).

The term "(meth) acrylic monomer" means a monomer having a (meth) acryloyl group.

The "(meth) acryloyl group" is a generic term for an acryloyl group and a methacryloyl group.

&Quot; (Meth) acrylate &quot; is a collective term for acrylate and methacrylate. "(Meth) acrylic acid" is a generic name of acrylic acid and methacrylic acid. "(Meth) acrylonitrile" is a generic term for acrylonitrile and methacrylonitrile. "(Meth) acrylamide" is a collective name of acrylamide and methacrylamide.

[(Meth) acrylic copolymer]

(Meth) acrylic copolymer (hereinafter also referred to as &quot; copolymer (A) &quot;) contained in the resin composition for a pressure-sensitive adhesive of the present invention satisfies the following formula (i). That is, the half width X of the one-dimensional scattering peak in the incineration X-ray scattering measurement is more than 0 and not more than 0.12. The half value width X is preferably 0.01 to 0.12, more preferably 0.03 to 0.11, still more preferably 0.05 to 0.10. When the full width at half maximum X is not more than the upper limit of the above range, the pressure-sensitive adhesive layer or the like using the copolymer (A) has a sufficient holding power and does not excessively increase the adhesive strength and can maintain an appropriate range, .

0 &lt; (i)

(Wherein X represents the half width of one-dimensional scattering peak in the measurement of incineration X-ray scattering of the copolymer (A)).

The incineration X-ray scattering measurement is a method of obtaining structure information of a nanoscale (1 to 100 nm) by observing scattered X-rays having a scattering angle of not more than a scattering angle. In the present invention, the half width X of one-dimensional scattering peak in the measurement of incineration X-ray scattering is used as an index of the (micro) phase separation state of the copolymer. Details of the measurement method of the half width X are as shown in the following embodiments.

A value having a half value width X means that a (micro) phase separation structure is formed in a sample (layer of a copolymer) to be subjected to incineration X-ray scattering measurement, that is, Quot; Usually, these plural portions each include a constituent unit having a different property.

Further, as the state of (micro) phase separation in a sample to be subjected to incineration X-ray scattering measurement becomes clearer or more uniform, the shape of the one-dimensional scattering peak becomes sharp and the half width X tends to decrease. That is, the smaller the half value width X, the lower the compatibility of a plurality of portions of the copolymer (A), indicating that (micro) phase separation is likely.

The constituent units having different properties are distributed in different portions, and the (micro) phase-separated structure is formed, so that the characteristics of each constituent unit are easily expressed. Therefore, it is possible to increase the cohesive force while maintaining an appropriate range of adhesive force, thereby improving the holding power and reducing the stain resistance of the substrate.

(Micro) phase separation structure may be a lamellar structure, a gyroid structure, a cylinder structure, a sphere structure, or the like, but any of these structures may be used.

The peak position Y of the one-dimensional scattering profile of the copolymer (A) is preferably 0.04 to 0.4.

The (meth) acrylic copolymer (A) preferably satisfies the following formula (ii). That is, it is preferable that the ratio of the half-width X of the one-dimensional scattering peak to the peak position Y of the one-dimensional scattering profile in the incineration X-ray scattering measurement is 0.1 to 0.50. X / Y is more preferably 0.1 to 0.43, and still more preferably 0.2 to 0.40. When X / Y is not less than the lower limit of the above range, the coating property is more excellent and the holding force is not excessively lowered. When X / Y is not more than the upper limit of the above range, the adhesive force in an appropriate range can be maintained, and the holding power and stain resistance on the substrate are more excellent.

The peak position Y represents the inter-domain distance of the micro-phase separation. When the distance between domains is narrowed, X / Y tends to be small.

0.1 < X / Y? (ii)

(Wherein X is as defined above and Y represents the peak position of the one-dimensional scattering profile in the measurement of the incinerated X-ray scattering of the copolymer (A).)

(Meth) acrylic copolymer (A) has a weight average molecular weight (Mw) of 1,000 to 1,000,000, preferably 50,000 to 700,000, more preferably 70,000 to 500,000, even more preferably 80,000 to 400,000, and most preferably 100,000 to 330,000 desirable. When the weight average molecular weight of the copolymer (A) is not lower than the lower limit of the above range, the pressure-sensitive adhesive layer having excellent holding power and low stain resistance to the substrate can be formed. When the weight average molecular weight of the copolymer (A) is not more than the upper limit of the above range, the resin composition for a pressure-sensitive adhesive containing the copolymer (A) and the coating composition are satisfactory.

The weight average molecular weight of the copolymer (A) is a value in terms of standard polystyrene measured by gel filtration chromatography (GPC). Specifically, it is measured by the method described in the following embodiments.

When the copolymer (A) is a 50 mass% ethyl acetate solution, the viscosity (hereinafter also referred to as &quot; solution viscosity &quot;) measured by a B-type viscometer at 25 ° C is preferably 10 to 800,000 mPa · s, More preferably from 200 to 7,000 mPa · s, still more preferably from 200 to 5,000 mPa · s, and most preferably from 500 to 3,500 mPa · s. If the solution viscosity is not lower than the lower limit of the above range, the adhesive force of the adhesive layer is more excellent and the stain resistance of the substrate becomes lower. When the solution viscosity is not more than the upper limit of the above range, the coatability, compatibility with other components in combination, and hot melt processability are more excellent.

The copolymer (A) may have a crosslinked structure or may not have a crosslinked structure. It is preferable that it does not have a cross-linking structure in view of coating properties such as the copolymer (A) and the resin composition for a pressure-sensitive adhesive containing it, compatibility with other components in combination, and hot melt processability.

The copolymer (A) includes a constituent unit derived from a (meth) acrylic monomer.

The content of the constituent unit derived from the (meth) acrylic monomer in the copolymer (A) is preferably from 20 to 100% by mass, more preferably from 40 to 40% by mass based on the total mass of the total constituent units constituting the copolymer (A) To 100% by mass.

One form of the copolymer (A) is a copolymer having a constituent unit derived from a macromonomer (a) having a number average molecular weight of 100 or more and 100,000 or less and a constituent unit derived from a vinyl monomer (b) ) &Quot;).

The copolymer (A1) typically has a structure of a graft copolymer or a block copolymer in which a polymer chain derived from a macromonomer (a) is bonded to a polymer chain composed of constituent units derived from a vinyl monomer (b).

In the copolymer (A1), the polymer chain derived from the macromonomer (a) and the polymer chain derived from the macromonomer (a) and the constituent unit derived from the vinyl monomer (b) Can be adjusted, and furthermore, the value of the full width at half maximum X can be adjusted.

Usually, the composition of the monomer constituting the macromonomer (a) and the composition of the vinyl monomer (b) are different. The composition represents the type and content of monomers.

Some or all of the structural units of the macromonomer (a) and the structural units derived from the vinyl monomer (b) are structural units derived from a (meth) acrylic monomer. The constituent unit derived from the (meth) acrylic monomer may be contained in either the constituent unit of the macromonomer (a) or the constituent unit derived from the vinyl monomer (b), or both constituent units may be included. Typically, it is included on both sides. The preferable range of the content of the constituent unit derived from the (meth) acrylic monomer in the copolymer (A1) is the same as the preferable range of the content of the constituent unit derived from the (meth) acrylic monomer in the copolymer (A).

&Lt; Macro monomer (a) >

The macromonomer (a) is a compound having two or more constitutional units derived from a monomer having a radically polymerizable group (hereinafter also referred to as &quot; monomer (a1) &quot;) and is a radically polymerizable group or a compound having a hydroxyl group, an isocyanate group, , An acid anhydride group, an amino group, an amide group, a thiol group, and a carbodiimide group.

The monomer (a1) will be described later in detail. The two or more structural units of the macromonomer (a) may be the same or different.

When the macromonomer (a) has the radically polymerizable group, the macromonomer (a) and the vinyl monomer (b) are copolymerized by radical polymerization to obtain the copolymer (A1).

When the macromonomer (a) has the above addition-reactive functional group, the vinyl monomer (b) usually has a functional group capable of reacting with the addition-reactive functional group. The copolymer (A1) can be obtained by reacting a functional group of the polymer containing the constituent unit derived from the vinyl monomer (b) with a macromonomer having the addition-reactive functional group.

Examples of the combination of the addition-reactive functional group and the functional group capable of reacting with the functional group include the following combinations.

A combination of a hydroxyl group and a carboxyl group or an acid anhydride group.

A combination of an isocyanate group and a hydroxyl group or a thiol group or a carboxyl group.

A combination of an epoxy group and an amino group.

A combination of a carboxyl group and an epoxy group or a carbodiimide group.

A combination of an amino group and a carboxyl group.

A combination of an amide group and a carboxyl group.

A combination of a thiol group and an epoxy group.

When the macromonomer (a) has a radical polymerizable group, the radical polymerizable group in the macromonomer (a) may be one or more, but preferably one. Even when the macromonomer (a) has the above addition-reactive functional group, the number of the above-mentioned additional reactive functional groups in the macromonomer (a) may be two or more, but preferably one.

The macromonomer (a) may have both a radically polymerizable group and either or both of the functional groups. In the case of having both the radical polymerizable group and the functional group, the radically polymerizable group of the macromonomer (a) and the functional groups may be one or more than two.

The macromonomer (a) may have a radical polymerizable group and the functional group in the interior of the repeating unit or may be contained in the terminal, but it is preferable that the macromonomer (a) has only a terminal at the end thereof because of easy adjustment of the viscosity of the resin composition for a pressure-

The macromonomer (a) preferably has a radical polymerizable group from the viewpoint of copolymerization with the vinyl monomer (b). When the copolymer (A1) is a copolymer of the macromonomer (a) and the vinyl monomer (b), the reaction product of the macromonomer having the functional group of the polymer containing the vinyl monomer (b) , It is excellent in that the introduction amount of the macromonomer (a) is easily controlled and the corrosion caused by the residual functional group can be reduced.

The radically polymerizable group of the macromonomer (a) is preferably a group having an ethylenic unsaturated bond. Examples of the group having an ethylenic unsaturated bond include CH ₂ ═C (COOR) -CH ₂ -, a (meth) acryloyl group, a 2- (hydroxymethyl) acryloyl group, and a vinyl group.

Wherein R is a hydrogen atom, an alkyl group having an unsubstituted or substituted group, an alicyclic group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, a heteroaryl group having an unsubstituted or substituted group, A nonaromatic heterocyclic group having a substituent, an aralkyl group having an unsubstituted or substituted group, an alkaryl group having an unsubstituted or substituted group, an organosilyl group having an unsubstituted or substituted group, or an unsubstituted or substituted group (Poly) organosiloxane group.

The unsubstituted alkyl group for R includes, for example, a branched or straight-chain alkyl group having 1 to 22 carbon atoms. Specific examples of the branched or linear alkyl group having 1 to 22 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, A decyl group, an undecyl group, an undecyl group, a dodecyl group (lauryl group), a heptyl group, a heptyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, , Octadecyl group (stearyl group), i-octadecyl group, nonadecyl group, eicosyl group and docosyl group, and the like can be given .

The unsubstituted alicyclic group in R may be monocyclic or polycyclic, and examples thereof include an alicyclic group having 3 to 20 carbon atoms. The alicyclic group is preferably a saturated alicyclic group, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a bicyclo [2.2.1] heptyl group, a cyclooctyl group and an adamantyl group And the like.

As the unsubstituted aryl group in R, for example, an aryl group having 6 to 18 carbon atoms can be mentioned. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group and a naphthyl group.

Examples of the unsubstituted heteroaryl group in R include a pyridyl group and a carbazolyl group.

Examples of the unsubstituted non-aromatic heterocyclic group include a pyrrolidinyl group, a pyrrolidone group, and a lactam group.

Examples of the unsubstituted aralkyl group include a benzyl group and a phenylethyl group.

Beach As the organo-silyl group ring, for example, -SiR ¹⁷ R ¹⁸ R ¹⁹ (wherein, R ¹⁷ to R ¹⁹ are alicyclic group, or unsubstituted with alkyl groups, unsubstituted or substituted with an unsubstituted or the substituents are each independently A ring or an aryl group having a substituent).

Examples of the unsubstituted or substituted alkyl group in R ¹⁷ to R ¹⁹ include the same ones as described above, and examples thereof include a methyl group, ethyl group, n-propyl group, n-butyl group, n- An n-octyl group, a n-dodecyl group, a stearyl group, a lauryl group, an isopropyl group, an isobutyl group, an s-butyl group, a 2-methylisopropyl group and a benzyl group. Examples of the unsubstituted or substituted alicyclic group include the same groups as described above, and examples thereof include a cyclohexyl group and the like. Examples of the aryl group having an unsubstituted or substituted group include the same groups as described above, and examples thereof include phenyl group, p-methylphenyl and the like. R ¹⁷ to R ¹⁹ may be the same or different.

Examples of the unsubstituted (poly) organosiloxane group include -SiR ³⁰ R ³¹ -OR ³² , - (SiR ³³ R ³⁴ -O-) _n -R ³⁵ wherein R ³⁰ to R ³⁵ each independently An unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, or an unsubstituted or substituted aryl group).

Examples of the unsubstituted or substituted alkyl group, alicyclic group and aryl group in R ³⁰ to R ³⁵ include the same ones as described above.

The substituent (s) in R (the alkyl group having a substituent, the alicyclic group having a substituent, the aryl group having a substituent, the heteroaryl group having a substituent, the nonaromatic heterocyclic group having a substituent, the aralkyl group having a substituent, An alkyl group (except when R is an alkyl group having a substituent), an aryl group, -COOR ¹¹ , a cyano group, -OR ¹² (a substituent in each of the organosilyl group having a substituent) , -NR ¹³ R ¹⁴ , -CONR ¹⁵ R ¹⁶ , a halogen atom, an allyl group, an epoxy group, a siloxy group, and a group showing hydrophilicity or ionicity.

Here, each of R ¹¹ to R ¹⁶ independently represents a hydrogen atom, an alkyl group having an unsubstituted or substituted group, an alicyclic group having an unsubstituted or substituted group, or an aryl group having an unsubstituted or substituted group. These groups may be the same as those described above.

The alkyl group and the aryl group in the above substituents may be the same as the above unsubstituted alkyl group or unsubstituted aryl group, respectively.

As the R ¹¹ of -COOR ^{11 in} the above substituent, a hydrogen atom or an unsubstituted alkyl group is preferable. That is, -COOR ¹¹ is preferably a carboxyl group or an alkoxycarbonyl group. The alkoxycarbonyl group includes, for example, a methoxycarbonyl group.

As the R ¹² of -OR ^{12 in} the above substituent, a hydrogen atom or an unsubstituted alkyl group is preferable. That is, -OR ¹² is preferably a hydroxy group or an alkoxy group. Examples of the alkoxy group include an alkoxy group having 1 to 12 carbon atoms, and specific examples thereof include a methoxy group.

Examples of -NR ¹³ R ¹⁴ in the above substituent include an amino group, a monomethylamino group, and a dimethylamino group.

Examples of -CONR ¹⁵ R ¹⁶ in the above substituent include a carbamoyl group (-CONH ₂ ), an N-methylcarbamoyl group (-CONHCH ₃ ), an N, N-dimethylcarbamoyl group (dimethylamido group: CON can be cited (CH _{3) 2)} or the like.

Examples of the halogen atom in the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the group exhibiting hydrophilicity or ionicity in the above substituent include an alkaline salt of a carboxyl group or an alkaline salt of a sulfoxy group, a poly (alkylene oxide) group such as a polyethylene oxide group and a polypropylene oxide group, And a cationic substituent group such as an ammonium salt group.

R is preferably an unsubstituted or substituted alkyl group or an unsubstituted or substituted alicyclic group, more preferably an unsubstituted alkyl group or an unsubstituted or substituted alicyclic group.

Among the above-mentioned ones, from the viewpoint of availability, it is preferable to use an alkyl group having 1 to 10 carbon atoms such as a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, Propyl group, n-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, isobornyl group and isobornyl group are preferable, and a methyl group, an ethyl group, An adamantyl group is more preferable.

The radically polymerizable group of the monomer (a1) is preferably a group having an ethylenically unsaturated bond, like the radically polymerizable group which the macromonomer (a) desirably has. That is, the monomer (a1) is preferably a vinyl monomer.

As the monomer (a1), various ones can be used, and examples thereof include the following.

(Meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- (Meth) acrylate, isoamyl (meth) acrylate, isoamyl (meth) acrylate, isonyl (meth) acrylate, isononyl (Meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (Meth) acrylate, isobornyl (meth) acrylate, 3,5,5-trimethylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl Pentenyl oxyethyl, terpene acrylates and derivatives thereof, hydrogenated rosin-acrylate or a derivative thereof, (meth) acrylate, a hydrocarbon group-containing (meth) acrylic acid ester of docosyl and the like;

(Meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate ester such as glycerol (meth) acrylate;

(Meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, (Meth) acryloyloxyethyl methacrylate, 2- (meth) acryloyloxyethyl methacrylate, 2- (meth) acryloyloxypropyl methacrylate, 2- Maleic acid monoethyl, monoethyl maleate, monoethyl maleate, monomethyl itaconate, monoethyl monoethyl itaconate, monoethyl itaconate, monoethyl maleate, itaconic acid monoacetate, Carboxyl group-containing vinyl monomers such as butyl, itaconamonooctyl, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monoctyl fumarate, and monoethyl citraconate;

Acid anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride;

(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (Meth) acrylamide, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylamide, N-methoxymethyl (Meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-vinylacetamide, maleic acid amide, Amide bond-containing cyclic vinyl monomers such as (meth) acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-epsilon-caprolactam and maleimide, and the like Amide bond-containing vinyl monomers;

Unsaturated dicarboxylic acid diester monomers such as dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dibutyl itaconate, and difluorocyclohexyl fumarate;

Epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate, glycidyl? -Ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate;

(Meth) acrylate ester-based vinyl monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;

(Meth) acrylate, divinylbenzene, divinylbenzene, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) Acrylate, triethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di , Neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylolpropane tri (meth) Polyfunctional vinyl monomers such as tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl (meth) acrylate, triallyl cyanurate, diaryl maleate, and polypropylene glycol diallyl ether;

Heterocyclic monomers such as vinyl pyridine and vinyl carbazole;

(Meth) acrylate, n-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, 3-methoxybutyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, t-butoxyethyl (meth) acrylate, ethoxyethoxyethyl (Caprolactone addition monomer, trade name) manufactured by Daicel Chemical Industries, Ltd.), methoxypolyethylene glycol methacrylate (ethylene glycol (trade name) manufactured by Nichiyu Corporation) (Trade name), &quot; Blemmer PME-200 &quot; (trade name, methoxypolyethylene glycol methacrylate (ethylene glycol) having a chain length of 4) manufactured by Nichiyu Corporation), &quot; Blemmer PME -400 &quot; (methoxypolyethylene glycol methacrylate manufactured by Nichifumi Co., Ltd. (ethylene Polypropylene glycol-methacrylate (the chain of ethylene glycol is 8 and the number of recurring units of propylene glycol is 9), "Blemmer 50 POEP-800B" (octoxypolyethylene glycol-polypropylene glycol- (Ethylene glycol-polypropylene glycol) monoacrylate, trade name), &quot; BLEMMER AME-100 &quot; (trade name) (Trade name) manufactured by Nippon Oil Corporation), "BLEMMER AME-200" (trade name, manufactured by Nichiyu Corporation) and "BLEMMER 50AOEP-800B" Monomers;

Acrylates such as 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyl Silane coupling agent-containing monomers such as trimethoxysilane and vinyltriethoxysilane;

(Meth) acrylate, trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl N-hexylsilyl (meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (meth) acrylate, triisopropylsilyl (Meth) acrylate, tri-t-butylsilyl (meth) acrylate, ethyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl Propyl-n-butylsilyl (meth) acrylate, n-octyldi-n-butylsilyl ) Acrylate, diisopropylstearylsilyl (meth) acrylate, dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, lauryldiphenylsilyl Tri-n-butylsilyl-n-butyl maleate, t-butyldiphenylsilylmethyl maleate, t-butyldiphenylsilyl-n-butyl maleate Butyldiphenylsilylmethyl fumarate, t-butyldiphenylsilylmethyl fumarate, tri-n-butylsilyl-n-butyl fumarate, t- (Trade name, manufactured by JNC Corporation), Silaplane FM-0721 (trade name, manufactured by JNC Co., Ltd.), Silaplane FM-0725 Plain TM-0701 (trade name, manufactured by JNC), Silaplane TM-0701T (trade name, manufactured by JNC Corporation), X-22-174ASX X-22-174BX (trade name, manufactured by Shinetsu Chemical Industry Co., Ltd.), KF-2012 (trade name, manufactured by Shinetsu Chemical Industry Co., Ltd.), X Containing organosilane other than the silane coupling agent-containing monomers such as -22-2426 (trade name, manufactured by Shinetsu Chemical Industry Co., Ltd.) and X-22-2404 (trade name, manufactured by Shinetsu Chemical Industry Co., Group-containing monomers;

Halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and chlorotrifluoroethylene;

Isocyanato group-containing monomers such as 2-isocyanatoethyl (meth) acrylate;

2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluorophenyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) (Perfluorobutyl) ethyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, (Meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 1H, (Meth) acrylate, 1H-pentafluoropentyl (meth) acrylate, 1H-octafluoropentyl (meth) acrylate, Hexafluorobutyl (meth) acrylate, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, Fluoromethyl) ethyl (meth) acrylate, and the like. (However, excluding a halogenated olefin);

(Meth) acrylate, 1- (cyclohexyloxy) ethyl methacrylate), 2-tetrahydropyranyl (meth) acrylate, ) Acrylate and the like;

Other vinyl monomers such as 4-methacryloyloxybenzophenone, styrene,? -Methylstyrene, vinyltoluene, (meth) acrylonitrile, vinyl chloride, vinyl acetate and vinyl propionate.

Among them, examples of the monomer (a1) used in the macromonomer (a) include methyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, -Hydroxyethyl, isobornyl methacrylate and cyclohexyl methacrylate are preferable in terms of enhancing retention of the pressure-sensitive adhesive.

The monomer (a1) may be used alone or in combination of two or more.

At least a part of the monomer (a1) is preferably a (meth) acrylic monomer.

The constituent unit derived from the monomer (a1) is preferably a constituent unit represented by the following formula (a ') (hereinafter also referred to as "constituent unit (a')"). That is, the macromonomer (a) preferably has two or more structural units (a ') having a radical polymerizable group.

(Wherein R ¹ represents a hydrogen atom, a methyl group or CH ₂ OH, and R ² represents OR ³ , a halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ , NHCOR ⁸ or R ⁹ ,

R ³ to R ⁸ are each independently a hydrogen atom, an alkyl group having an unsubstituted or substituted group, an alicyclic group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, a heteroaryl having an unsubstituted or substituted group A nonaromatic heterocyclic group having an unsubstituted or substituted group, an aralkyl group having an unsubstituted or substituted group, an alkaryl group having an unsubstituted or substituted group, an organosilyl group having an unsubstituted or substituted group, (Poly) organosiloxane group having a substituent, and the substituents in these groups are each an alkyl group, an aryl group, a heteroaryl group, a nonaromatic heterocyclic group, an aralkyl group, an alkaryl group, a carboxylic acid group (COOH) (SO ₃ H), and a halogen atom, which may be the same or different from each other, and are each independently selected from the group consisting of a hydroxyl group, a carboxylate group, an epoxy group, a hydroxyl group, an alkoxy group, a primary amino group, a secondary amino group, a tertiary amino group, an isocyanato group, R ⁹ represents an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, or a nonaromatic heterocyclic group having an unsubstituted or substituted group, , The substituents in these groups are each an alkyl group, an aryl group, a heteroaryl group, a nonaromatic heterocyclic group, an aralkyl group, an alkaryl group, a carboxylic acid group, a carboxylic acid ester group, an epoxy group, a hydroxy group, , A secondary amino group, a tertiary amino group, an isocyanato group, a sulfonic acid group, an alkyl group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, an olefin group having an unsubstituted or substituted group and a halogen atom . &Lt; / RTI &gt;

R ³ to unsubstituted alkyl group, an unsubstituted alicyclic group, an unsubstituted aryl group, an unsubstituted heteroaryl group, an unsubstituted non-aromatic heterocyclic group, unsubstituted aralkyl groups in R ^8, unsubstituted The alkaryl group, the unsubstituted organosilyl group and the unsubstituted (poly) organosiloxane group are the same as those exemplified in the above-mentioned R, respectively.

The substituent in R ³ to R ⁸ (an alkyl group having a substituent, an alicyclic group having a substituent, an aryl group having a substituent, a heteroaryl group having a substituent, a nonaromatic heterocyclic group having a substituent, an aralkyl group having a substituent, An alkyl group, an aryl group, a heteroaryl group, a nonaromatic heterocyclic group, an aralkyl group, an alkaryl group and a halogen atom in the substituent group of the alkaryl group having a substituent, &Lt; / RTI &gt;

Examples of the carboxylic acid ester group include groups in which R ^{11 in} -COOR ¹¹ is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, or an unsubstituted or substituted aryl group have.

As the alkoxy group, there can be mentioned a group in which the R ¹² of -OR ¹² is an unsubstituted alkyl group.

Examples of the secondary amino group include a group represented by -NR ¹³ R ¹⁴ wherein R ¹³ is a hydrogen atom, R ¹⁴ is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, or an unsubstituted or substituted aryl group .

As the tertiary amino group, in the -NR ¹³ R ¹⁴ in R ¹³ and R ¹⁴ are each an aryl group having a beach alicyclic group, or unsubstituted or substituent having an alkyl group, an unsubstituted or a substituent having a ring or a substituent group .

The unsubstituted aryl group, unsubstituted heteroaryl group and unsubstituted non-aromatic heterocyclic group in R ⁹ may be the same as described above.

Among the substituents (the aryl group having a substituent, the heteroaryl group having a substituent, and the substituent in each of the non-aromatic heterocyclic groups having a substituent) in R ⁹ , a carboxylic acid ester group, an alkoxy group, a primary amino group, A secondary amino group, a tertiary amino group, an alkyl group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, and a halogen atom are the same as described above.

Examples of the unsubstituted olefin group include an allyl group and the like.

Examples of the substituent in the substituent-containing olefin group include the same substituents as those in R ⁸ .

The structural unit (a ') is a structural unit derived from CH ₂ = CR ¹ R ² .

Specific examples of CH ₂ = CR ¹ R ² include the following.

(Meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n- Butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate, i-stearyl (meth) acrylate, i-decyl (meth) acrylate, (Meth) acrylate], substituted or unsubstituted aralkyl (meth) acrylates (e.g., benzyl (meth) acrylate, Acrylate, m-methoxyphenylethyl (meth) acrylate, p-methoxyphenylethyl (meth) acrylate], substituted or unsubstituted (Meth) acrylate, p-methoxyphenyl (meth) acrylate, o-methoxyphenylethyl (meth) acrylate, (Meth) acrylate], halogen atom-containing (meth) acrylate [for example, trifluoroethyl (meth) acrylate] such as isobornyl (meth) acrylate, cyclohexyl (Meth) acrylate monomers containing a minor group such as (meth) acrylate, perfluorooctyl (meth) acrylate and perfluorocyclohexyl (meth) acrylate;

(Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (Meth) acrylate monomer having an oxyethylene group such as methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate and 2- (2-ethylhexaoxy) ethyl ;

(Meth) acrylic acid ester monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and glycerol (meth) acrylate;

Methoxypolyethylene glycol allyl ether, methoxypolypropylene glycol allyl ether, butoxypolyethylene glycol allyl ether, butoxypolypropylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl ether, Terminal alkoxy allylated polyether monomers such as ether;

Epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate, glycidyl? -Ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate;

(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (Meth) acrylamide, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylamide, N-methoxymethyl (Meth) acrylamide, N, N'-methylenebis (meth) acrylamide, N, N-dimethylaminoethyl Amide bond-containing vinyl monomers such as (meth) acryloylmorpholine, N-vinylpyrrolidone and N-vinyl-epsilon -caprolactam;

Butylaminoethyl (meth) acrylate, and other primary or secondary amino group-containing vinyl monomers;

(Meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate and dibutylaminoethyl An amino group-containing vinyl monomer;

Heterocyclic basic monomers such as vinyl pyridine and vinyl carbazole;

(Meth) acrylate, trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl N-hexylsilyl (meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (meth) acrylate, triisopropylsilyl (Meth) acrylate, tri-t-butylsilyl (meth) acrylate, ethyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl Propyl-n-butylsilyl (meth) acrylate, n-octyldi-n-butylsilyl (Meth) acrylate, diisopropylstearylsilyl (meth) acrylate, dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl An organosilyl group-containing vinyl monomer;

(Meth) acrylate, monohydroxybutyl (meth) acrylate, tetrahydrophthalic acid monohydroxybutyl (meth) acrylate, phthalic acid mono (meth) acrylate, tetrahydrophthalic acid monohydroxypropyl (Meth) acrylate, monohydroxyethyl (meth) acrylate, monohydroxypropyl (meth) acrylate, monohydroxyethyl (meth) acrylate, monohydroxyethyl ) Acrylate, maleic acid monohydroxypropyl (meth) acrylate and the like, ethylenically unsaturated monomers containing a carboxyl group;

Cyano group-containing vinyl monomers such as acrylonitrile and methacrylonitrile;

Alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and 2-ethylhexyl vinyl ether), cycloalkyl vinyl ethers (such as cyclohexyl vinyl ether) Vinyl ether monomers;

Vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Aromatic vinyl monomers such as styrene, vinyl toluene, and? -Methyl styrene;

Halogenated olefins such as vinyl chloride and vinyl fluoride; Etc.

The macromonomer (a) may further have another structural unit other than the structural unit (a '). As the other constituent unit, for example, a constituent unit derived from a monomer which does not correspond to CH ₂ = CR ¹ R ² among the monomers exemplified as the above-mentioned monomer (a1) can be mentioned.

Specific preferred examples of other structural units include the following structural units derived from a monomer.

Tri-n-butylsilyl-n-butyl maleate, t-butyldiphenylsilylmethyl maleate, t-butyldiphenylsilyl-n-butyl maleate Butyldiphenylsilylmethyl fumarate, t-butyldiphenylsilylmethyl fumarate, tri-n-butylsilyl-n-butyl fumarate, t- Organosilyl group-containing vinyl monomers such as butyl fumarate;

Acid anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride;

But are not limited to, crotonic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate, maleamoyloctyl maleate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, Ethylenically unsaturated monomers containing carboxyl groups such as monomethyl fumarate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monoctyl fumarate and monoethyl citraconate;

Unsaturated dicarboxylic acid diester monomers such as dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dibutyl itaconate, and difluorocyclohexyl fumarate;

Halogenated olefins such as vinylidene chloride, vinylidene fluoride and chlorotrifluoroethylene;

Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9- (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl methacrylate, triallyl cyanurate, maleic acid diallyl, polypropylene glycol diallyl Polyfunctional monomers such as ethers.

The macromonomer (a) preferably contains 50 mass% or more of the constituent unit derived from the (meth) acrylic monomer with respect to the total mass (100 mass%) of the total constituent units constituting the macromonomer (a) By mass or more. The upper limit is not particularly limited and may be 100% by mass.

As the constituent unit derived from the (meth) acrylic monomer, a constituent unit in which R ¹ in the formula (a ') is a hydrogen atom or a methyl group and R ² is COOR ⁵ is preferable.

As the macromonomer (a), a macromonomer into which a radical polymerizable group is introduced at the end of the main chain containing at least two constituent units (a ') is preferable, and a macromonomer represented by the following formula (1) is more preferable. By using the macromonomer of this structure, it is possible to form a pressure-sensitive adhesive layer having excellent holding power and low stain on substrate.

(Wherein R represents a hydrogen atom, an alkyl group having an unsubstituted or substituted group, an alicyclic group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, a heteroaryl group having an unsubstituted or substituted group, A non-aromatic heterocyclic group having a substituted or substituted group, an aralkyl group having an unsubstituted or substituted group, an alkaryl group having an unsubstituted or substituted group, an organosilyl group having an unsubstituted or substituted group, (Poly) organosiloxane group having a substituent, Q represents a main chain portion containing two or more structural units (a '), and Z represents a terminal group.

In the formula (1), R is the same as R in the above-mentioned CH ₂ C (COOR) -CH ₂ -, and preferred embodiments are also the same.

The two or more structural units (a ') contained in Q may be the same or different.

Q may be composed only of the constituent unit (a '), or may further comprise constituent units other than the constituent unit (a').

Q is a structural unit (a '), and it is preferable that R ¹ in the formula (a') is a hydrogen atom or a methyl group, and R ² is COOR ⁵ . The proportion of the constituent unit is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 100% by mass, based on the total mass of the total constituent units constituting Q (100% by mass).

The number of the constituent units constituting Q can be appropriately set within a range in which the number average molecular weight of the macromonomer (a) falls within the above range.

Z may be, for example, a hydrogen atom, a group derived from a radical polymerization initiator, or a radical polymerizable group, in the same manner as the terminal group of a polymer obtained by a known radical polymerization.

As the macromonomer (a), a macromonomer represented by the following formula (2) is particularly preferable.

(Wherein R and Z are the same as defined above, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a hydrogen atom, an alkyl group having an unsubstituted or substituted group, an alicyclic group having an unsubstituted or substituted group, An unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted nonaromatic heterocyclic group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted group , An unsubstituted or substituted organosilyl group, an unsubstituted or substituted (poly) organosiloxane group, and a substituent in these groups are each an alkyl group, an aryl group, a heteroaryl group, a bis An aromatic heterocyclic group, an aralkyl group, an alkaryl group, a carboxylic acid group, a carboxylic acid ester group, an epoxy group, a hydroxy group, an alkoxy group, a primary amino group, a secondary amino group, Is at least one member selected from clay or a cyano, sulfonic acid group and halogen atom, the group consisting of, n denotes a natural number equal to or greater than 2, Z represents a terminal group.)

In the formula (2), R and Z are the same as described above.

Each group in R ²² is the same as that exemplified for R ⁵ in COOR ⁵ .

n is a natural number of 2 or more. n is preferably such a range that the number average molecular weight (Mn) of the macromonomer (a) is 100 or more and 100,000 or less. A preferable range of the number average molecular weight is as follows. The n R ^{21 s} may be the same or different. The n number of R &lt; ²² &gt; s may be the same or different.

When the macromonomer (a) has the addition-reactive functional group and the macromonomer is added to the functional group of the polymer containing the constituent unit derived from the vinyl monomer (b), the macromonomer (a) , And it is preferable to have two or more of the above-mentioned structural units (a '). As the structural unit (a '), the same monomer units as those in the case where the macromonomer (a) has a radical polymerizable group can be used.

In addition to the macromonomer (a), the compound having a functional group may be added to the functional group of the polymer containing the constituent unit derived from the vinyl monomer (b). Examples of the compound having a functional group include X-22-173BX (trade name, manufactured by Shinetsu Chemical Industry Co., Ltd.), X-22-173DX (trade name, manufactured by Shinetsu Chemical Industry Co., -170BX (trade name, manufactured by Shinetsu Chemical Industries, Ltd.), X-22-170DX (trade name, manufactured by Shinetsu Chemical Industry Co., Ltd.), X-22-176DX (Shinetsu Chemical Industries Co., X-22-176F (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and X-22-173GX-A (trade name, manufactured by Shinetsu Chemical Industry Co., Ltd.) Silicone compounds and the like.

The number average molecular weight (Mn) of the macromonomer (a) is preferably 100 to 100,000, more preferably 800 to 30,000, further preferably 900 to 10,000, particularly preferably 1,000 to 6,000, and most preferably 1,000 to 5,000 desirable. When the number average molecular weight of the macromonomer (a) is not lower than the lower limit of the above range, the holding strength of the pressure-sensitive adhesive layer is more excellent. When the number average molecular weight of the macromonomer (a) is not more than the upper limit of the above range, the adhesive strength of the pressure-sensitive adhesive layer becomes an appropriate value and the compatibility with other components and the hot melt processability when the pressure-sensitive adhesive composition is formed into a pressure-sensitive adhesive composition are excellent.

The number average molecular weight of the macromonomer (a) is measured by gel filtration chromatography (GPC) using polystyrene as a reference resin.

The glass transition temperature (hereinafter also referred to as &quot; Tga &quot;) of the macromonomer (a) is preferably 0 to 150 ° C, more preferably 10 to 120 ° C, and still more preferably 30 to 100 ° C. When Tga is not less than the lower limit of the above range, the adhesive force of the adhesive layer is more excellent. When Tga is not more than the upper limit of the above range, the hot melt processability is more excellent.

Tga can be measured with a differential scanning calorimeter (DSC).

Tga can be adjusted by the composition and the like of the monomer forming the macromonomer (a).

The macromonomer (a) may be one prepared by a known method, or a commercially available macromonomer (a) may be used.

Examples of the method for producing the macromonomer (a) having a radical polymerizable group include a method of producing a macromonomer (a) having a radically polymerizable group, for example, a method of using a cobalt chain transfer agent, a method of using an? -Methylstyrene dimer, A method of using it, a method of chemically bonding a radical polymerizable group to a polymer, a method of pyrolysis, and the like.

Among these methods, a method of producing a macromonomer (a) having a radically polymerizable group is preferably a method of producing a macromonomer (a) using a cobalt chain transfer agent because the number of production steps is small and the chain transfer constant of the catalyst used is high. Further, the macromonomer (a) when it is produced by using a cobalt chain transfer agent has the structure represented by the above formula (1).

Examples of the method for producing the macromonomer (a) using a cobalt chain transfer agent include an aqueous dispersion polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method. From the viewpoint of the simple recovery process, the aqueous dispersion polymerization method is preferable.

As a method for chemically bonding the radical polymerizable group to the polymer, for example, there are a method of preparing by substituting a halogen group of a polymer having a halogen group with a compound having a radical polymerizable carbon-carbon double bond, a method of producing a vinyl monomer having an acid group and an epoxy group A method of reacting a vinyl polymer having an epoxy group with a vinyl monomer having an acid group, a method of reacting a vinyl polymer having a hydroxyl group with a diisocyanate compound to obtain an isocyanate group-containing vinyl polymer, A method of reacting a vinyl-based polymer with a vinyl monomer having a hydroxyl group, and the like, and any method may be used.

The number average molecular weight of the macromonomer (a) can be adjusted by a polymerization initiator, a chain transfer agent, and the like.

Examples of the method for producing the macromonomer (a) having an addition-reactive functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, an amino group, an amide group, a thiol group or a carbodiimide group include, A method of using a chain transfer agent such as mercaptoethanol, mercaptoacetic acid or mercaptopropionic acid; a method of using 2,2'-azobis (propane-2-carboamidine), 4,4 ' Azo compounds such as azobis (4-cyanovaleric acid), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine], 2,2 'azobis [2- [ Hydroxyethyl) 2-imidazoline 2-yl] propane] can be used as the initiator.

&Lt; Vinyl monomer (b) >

The vinyl monomer (b) is a monomer other than a macromonomer having an ethylenic unsaturated bond. The vinyl monomer (b) is not particularly limited, and the same monomer (a1) for obtaining the macromonomer (a) exemplified above can be used. The vinyl monomer (b) may be used alone or in combination of two or more.

It is preferable that at least a part of the vinyl monomer (b) is a (meth) acrylic monomer.

When the macromonomer (a) is added to a polymer containing a constituent unit derived from the vinyl monomer (b), the vinyl monomer (b) includes those having a functional group capable of reacting with the functional group of the macromonomer (a) Suitable.

The vinyl monomer (b) preferably contains an alkyl (meth) acrylate having an unsubstituted alkyl group having 8 to 30 carbon atoms (hereinafter also referred to as &quot; monomer (b1) &quot;). By the monomer (b1), the flexibility as a pressure-sensitive adhesive can be exhibited, or the pressure-sensitive adhesive force can be maintained in an appropriate range, and the pressure-sensitive adhesive residue can be suppressed. Further, since the monomer (b1) is hydrophobic, the absorption rate can be suppressed or the relative dielectric constant can be reduced by the monomer (b1). When the copolymer (A1) is used in a resin composition for a pressure-sensitive adhesive containing a polymerizable monofunctional compound such as a resin composition (1) for a pressure-sensitive adhesive described below, the vinyl monomer (b) contains the monomer , The copolymer (A1) and the polymerizable monofunctional compound are more excellent in compatibility. That is, as a polymerizable monofunctional compound, a polymerizable monofunctional compound having a hydrocarbon group having 8 or more carbon atoms is often used, as described later in detail. Since the monomer (b1) has an alkyl group having 8 to 30 carbon atoms, the copolymer (A1) contains a constituent unit derived from the monomer (b1), so that compatibility with such a polymerizable monofunctional compound is enhanced. When the compatibility of the copolymer (A1) with the polymerizable monofunctional compound is high, the transparency of the pressure-sensitive adhesive layer formed from the resin composition for a pressure-sensitive adhesive becomes higher and the transparent double-faced pressure-sensitive adhesive sheet called OCA (Optical Clear Adhesive) Which is required for optical transparency such as a liquid transparent pressure-sensitive adhesive.

Specific examples of the monomer (b1) include, but are not limited to, 2-ethylhexyl methacrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) Decyl, isodecyl (meth) acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate and behenyl (meth) acrylate.

The number of carbon atoms of the alkyl group of the monomer (b1) is preferably from 8 to 30, and particularly preferably from 9 to 18.

The vinyl monomer (b) may further contain a vinyl monomer other than the monomer (b1), if necessary. As the other vinyl monomer, it is possible to appropriately select among the monomers exemplified above.

For example, it may contain at least one monomer selected from the group consisting of methyl (meth) acrylate and ethyl (meth) acrylate from the viewpoint of enhancing the cohesive force of the pressure-sensitive adhesive.

An amide bond-containing vinyl monomer may be included from the viewpoint of enhancing adhesion, anti-wet heat whitening property and low corrosion resistance. The term "wet heat whitening" refers to a property that the adhesive layer is hardly whitened when exposed to a high temperature and high humidity atmosphere. Examples of the amide bond-containing vinyl monomers include the same ones as described above.

Other preferable vinyl monomers include (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, styrene, isobornyl (meth) acrylate, cyclohexyl Benzyl acrylate, and tetrahydrofurfuryl (meth) acrylate.

The composition of the vinyl monomer (b) differs from the composition of the monomers constituting the macromonomer (a), as described above.

The vinyl monomer (b) preferably has a composition in which a difference in polarity is generated between a polymer obtained by polymerizing only the vinyl monomer (b) (hereinafter also referred to as "polymer (B)") and the macromonomer (a). If there is a polarity difference between the polymer (B) and the macromonomer (a), the half value width X tends to fall within the above range. When the half-value width X is within the above range, the polymer chain of the macromonomer (a) and the polymer chain formed from the polymer (B) are micro-phase-separated when the pressure-sensitive adhesive layer or the coating film is formed. For example, the effect of improving the holding power of the adhesive layer by the macromonomer (a) is sufficiently exhibited, and the holding power of the adhesive layer is excellent.

As an example of the composition in which a difference in polarity occurs, examples in which the macromonomer (a) contains a structural unit derived from methyl methacrylate and the vinyl monomer (b) includes the monomer (b1) can be cited. The monomer (b1) has a lower polarity than methyl methacrylate because the alkyl group has a larger number of carbon atoms. With such a composition, a difference in polarity between the polymer (B) and the macromonomer (a) is generated.

In this example, the proportion of the constitutional unit derived from methyl methacrylate to the total of all the constitutional units constituting the macromonomer (a) is preferably 50% by mass or more, and more preferably 75% by mass or more. The proportion of the monomer (b1) relative to the total amount of the vinyl monomer (b) is preferably 30 mass% or more, more preferably 60 mass% or more, further preferably 80 mass% or more, desirable. The ratio of the structural units derived from the methacrylic acid methyl group in the macromonomer (a) or the proportion of the monomer (b1) in the vinyl monomer (b) The difference in polarity of the adhesive is liable to be micro-phase-separated, so that the pressure-sensitive adhesive layer retaining ability is excellent and adhesive residue is hardly generated.

In this example, the content of the vinyl monomer having a polar functional group such as a carboxyl group, a hydroxyl group, an amide group, and an amino group in the vinyl monomer (b) is preferably such that the total content of the vinyl monomer (b) Is preferably 30 mass% or less, more preferably 10 mass% or less, and further preferably 5% or less. The lower limit is not particularly limited and may be 0% by mass.

The vinyl monomer (b) preferably has a composition such that the polymer (B) obtained by polymerizing only the vinyl monomer (b) has a glass transition temperature (TgB) of -100 to 10 ° C. TgB is preferably -65 to 0 占 폚, more preferably -60 to -10 占 폚. When the TgB is within the above range, the resin composition for a pressure-sensitive adhesive comprising the copolymer (A1) has appropriate flexibility and adhesiveness.

TgB is the glass transition temperature of the homopolymer of the vinyl monomer when the vinyl monomer (b) is one, and when the vinyl monomer (b) is plural types, the glass transition temperature and the glass transition temperature of the homopolymer of each of the plural vinyl monomers Means the value calculated from Fox's formula from the mass fraction.

The calculation formula of Fox is a calculated value obtained by the following formula and can be obtained by using the value described in the polymer handbook [Polymer Handbook, J. Brandrup, Interscience, 1989] (Tg in the formula corresponds to TgB box).

1 / (273 + Tg) =? (Wi / (273 + Tgi)) where Wi is the mass fraction of monomer i and Tgi is the glass transition temperature (占 폚) of the homopolymer of monomer i.

It is preferable that Tga and TgB described above have a relationship represented by the following formula (3) because they can sufficiently express the characteristics of each of the moiety including the macromonomer (a) moiety and the constituent unit derived from the vinyl monomer (b) Do. That is, it is preferable that Tga-TgB> 0 占 폚.

Tga> TgB ... (3)

More preferably Tga-TgB > 50 DEG C, and most preferably Tga-TgB > 80 DEG C.

&Lt; Content of each constituent unit >

The content of the constituent unit derived from the macromonomer (a) in the copolymer (A1) is preferably from 3 to 60 mass%, more preferably from 7 to 40 mass%, based on the total mass of all the constituent units constituting the copolymer (A1) , More preferably from 8 to 30 mass%, and particularly preferably from 9 to 20 mass%. If the content of the constituent unit derived from the macromonomer (a) is not lower than the lower limit of the above range, the pressure-sensitive adhesive layer holding power is more excellent. When the content of the constituent unit derived from the macromonomer (a) is not more than the upper limit of the above range, the coatability and compatibility with other components in combination and hot melt processability are better.

The content of the constituent unit derived from the vinyl monomer (b) in the copolymer (A1) is preferably from 40 to 97% by mass, more preferably from 60 to 93% by mass, based on the total mass of all the constituent units constituting the copolymer (A1) , More preferably from 70 to 92 mass%, and particularly preferably from 80 to 91 mass%. When the content of the constitutional unit derived from the vinyl monomer (b) is not lower than the lower limit of the above-mentioned range, the compatibility with the other components and the hot melt processability in the formulations are more excellent. If the content of the constitutional unit derived from the vinyl monomer (b) is not more than the upper limit of the above range, the pressure-sensitive adhesive layer holding power is more excellent.

&Lt; Process for producing copolymer (A1)

Examples of the method for producing the copolymer (A1) include the following production methods (?) And (?). The copolymer (A1) may be the one produced by the production method (?) Or the one produced by the production method (?). However, the production method of the copolymer (A1) is not limited to these.

Production method (?): As the macromonomer (a), a macromonomer having a radical polymerizable group is used, and the macromonomer (a) and the vinyl monomer (b) are copolymerized.

Production method (?): As the macromonomer (a), a macromonomer having the addition-reactive functional group is used, and the macromonomer (a) and the vinyl monomer containing a vinyl monomer having a functional group capable of reacting with the addition- (b) a structural unit derived from the polymer.

By adjusting the number average molecular weight of the macromonomer (a), the composition of the monomer constituting the macromonomer (a), the composition of the vinyl monomer (b), the weight average molecular weight of the copolymer (A1) The copolymer (A1) in which the half value width X satisfies the above formula (i) is obtained by adjusting the compatibility of the polymer chain derived from the macromonomer (a) and the polymer chain composed of the constituent unit derived from the vinyl monomer (b) Loses.

For example, as described above, the difference in polarity between the macromonomer (a) and the polymer (B) obtained by polymerizing only the vinyl monomer (b) affects the compatibility. The greater the difference in polarity, the lower the compatibility and the smaller the half width X. Further, the larger the number average molecular weight of the macromonomer (a) or the weight average molecular weight of the copolymer (A1), the smaller the half value width X tends to be.

The solubility parameter delta a of the constitutional unit derived from the macromonomer (a) and the solubility parameter delta b of the constitutional unit derived from the vinyl monomer (b) are in the range of ( ? a -? b) > 0. That is, it is preferable that the difference between? A and? B is greater than zero. (? a-? b)? 0.30 is more preferable, and it is more preferable that (? a-? b)? 0.60 is satisfied.

The solubility parameter? Is obtained by the following formula (I).

隆 = 裡 (mi 隆 i) ... (I)

In the formula (I), mi represents the molar fraction of monomer i constituting the constitutional unit derived from the macromonomer (a) or the constitutional unit derived from the vinyl monomer (b), and delta i indicates the solubility parameter of the monomer i.

? In the case where the monomer i constitutes the constituent unit derived from the macromonomer (a) is? A and the monomer i constitutes the constituent unit derived from the vinyl monomer (b).

Further, the solubility parameter (? I) of the monomer (i) can be calculated from the following formula (II).

? i = {? (njEj) /? (njVj)} 1/2 ... (II)

In the formula (II), nj denotes the number of atomic j constituting the monomer i, Ej denotes the aggregation energy (J / mol) of the atomic group j and Vj denotes the molar volume (cm ³ / mol) . Also, Ej and Vj are described in RF Fedors, Polym. Eng. Sci. &Quot;, (1974). When the solubility parameter? A of the constitutional unit derived from the macromonomer (a) in the copolymer (A) and the solubility parameter? B of the constitutional unit derived from the vinyl monomer (b) satisfy the above requirements and the half width X is in the range of more than 0 and 0.12 or less , The pressure-sensitive adhesive layer using the copolymer (A) maintains an appropriate adhesive force and maintains a good holding force.

Further, the ratio of X / Y can be adjusted by the amount of the polymer chain derived from the macromonomer (a) or the number average molecular weight. Concretely, when the amount of the polymer chain derived from the macromonomer (a) is increased or the number average molecular weight of the polymer chain derived from the macromonomer (a) is made small, X / Y tends to be small.

As the production method of the copolymer (A1), the production method (?) Is preferred. That is, the copolymer (A1) is preferably a copolymer of the macromonomer (a) and the vinyl monomer (b). In such a copolymer, the constitutional unit derived from the macromonomer (a) and the constitutional unit derived from the vinyl monomer (b) are randomly arranged. That is, a polymer chain derived from at least one macromonomer (a) is bonded throughout the main chain of the copolymer (A1). These polymerizers have a tendency that the holding power of the pressure-sensitive adhesive layer becomes better as compared with, for example, a case where the constitutional unit derived from the macromonomer (a) is bonded only to the end of the polymer chain containing the constituent unit derived from the vinyl monomer have.

(Production method (?))

The preferable range of the composition of the monomer to be polymerized in the production method (?), That is, the content of each monomer (mass%) (input amount) to the kind of the monomer to be polymerized and the total mass of the total monomers, , That is, the kind of the constituent unit derived from the monomer constituting the copolymer (A1) and the content (mass%) of each constituent unit with respect to the total mass of the total constituent units.

For example, the content of the macromonomer (a) relative to the total mass (100 mass%) of the total monomers to be polymerized is preferably 3 to 60 mass%, more preferably 7 to 40 mass%, and more preferably 8 to 30 mass% , More preferably from 9 to 20 mass%.

The polymerization of the monomer may be carried out by a known method using a known polymerization initiator. For example, the macromonomer (a) and the vinyl monomer (b) may be reacted in the presence of a radical polymerization initiator at a reaction temperature of 60 to 120 캜 for 1 to 14 hours. In the polymerization, a chain transfer agent may be used if necessary.

As the polymerization method, known polymerization methods such as solution polymerization method, suspension polymerization method, bulk polymerization method, emulsion polymerization method and the like can be applied. From the viewpoint of drying properties and coating performance in the film-forming step, it is preferable that the resin composition for a pressure-sensitive adhesive containing the copolymer (A) does not contain water. The water content in the pressure-sensitive adhesive resin composition is preferably 10 mass% or less, more preferably 5 mass% or less, and most preferably 1 mass% or less. The water content in the resin composition for a pressure-sensitive adhesive can be measured by the Karl Fischer method. Further, in order to reduce the water content in the resin composition for a pressure-sensitive adhesive, it is preferable that water is not contained in the production process of the copolymer (A). The water content in the production process of the copolymer (A) is preferably 10% by mass or less, more preferably 5% by mass or less, most preferably 1% by mass or less and 0% by mass. A solution polymerization method is preferable as a production method which does not include water in the production process of the copolymer (A).

The solution polymerization can be carried out, for example, by supplying a polymerization solvent, a monomer, and a radical polymerization initiator into a polymerization vessel and maintaining the polymerization temperature at a predetermined reaction temperature. The monomer may be added to the polymerization vessel in advance (before the inside of the polymerization vessel is brought to a predetermined reaction temperature), or the dropwise feed may be performed after the polymerization vessel is heated to a predetermined reaction temperature. , And the remaining portion may be dropped and supplied.

The copolymer (A) has a weight average molecular weight of 1,000 to 1,000,000 and satisfies the above formula (i), thereby forming a pressure-sensitive adhesive layer having a sufficient holding power and an appropriate range of adhesion, can do. A sufficient holding force and an appropriate range of adhesive force are unlikely to cause problems such as positional deviation after the members are bonded together via the adhesive layer. When the protective sheet is provided with the adhesive layer, the protective sheet is easily peeled off and the substrate is not easily contaminated after peeling off.

The copolymer (A) is useful for a resin composition for a pressure-sensitive adhesive in that it exhibits the above effect. In particular, it is suitably used as a pressure-sensitive adhesive sheet.

However, the use of the copolymer (A) is not limited to the above, and may be used for other purposes. Examples of other uses include a coating composition, a resin composition for an adhesive, a composition for a molding material, and a composition for a film.

[Resin composition for pressure-sensitive adhesive]

The resin composition for a pressure-sensitive adhesive of the present invention comprises the copolymer (A).

The copolymer (A) contained in the resin composition for a pressure-sensitive adhesive may be one kind or two or more kinds. The resin composition for a pressure-sensitive adhesive of the present invention may be composed solely of the (meth) acrylic copolymer (A), and may contain other components as required.

&Lt; Polymerizable monofunctional compound >

The resin composition for a pressure-sensitive adhesive of the present invention may further contain, if necessary, a polymerizable monofunctional compound having one radically polymerizable group.

The radically polymerizable group in the polymerizable monofunctional compound may be the same as those described above, and a (meth) acryloyl group is preferable. That is, the polymerizable monofunctional compound is preferably a monofunctional (meth) acrylate having one (meth) acryloyl group.

As the polymerizable monofunctional compound, the same monomer as that for obtaining the macromonomer (a) exemplified above can be used.

As the polymerizable monofunctional compound, a polymerizable monofunctional compound having a hydrocarbon group having 4 or more carbon atoms is preferable from the viewpoint of flexibility as a pressure-sensitive adhesive. Examples of the hydrocarbon group include an alkyl group, an aryl group, and an aralkyl group. And the number of carbon atoms of the corresponding hydrocarbon group is more preferably 8 to 30. [

When the resin composition for a pressure-sensitive adhesive of the present invention is a resin composition for a liquid-phase pressure-sensitive adhesive, the polymerizable monofunctional compound preferably functions as a reactive diluent. As the polymerizable monofunctional compound functioning as a reactive diluent, a polymerizable monofunctional compound which is liquid at 25 占 폚 is typically used. As such a polymerizable monofunctional compound, the same polymerizable monofunctional compound as the monomer for obtaining the macromonomer (a) may be used, either alone or in combination of two or more.

Examples of the polymerizable monofunctional compound include isodecyl (meth) acrylate, isostearyl (meth) acrylate, ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl At least one member selected from the group consisting of nonyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate and lauryl acrylate is particularly preferable.

<Oligomer component>

The resin composition for a pressure-sensitive adhesive of the present invention may further comprise an oligomer component, if necessary.

Examples of the oligomer component include a urethane oligomer, a polyester oligomer, an acrylic oligomer, a polyether oligomer, and a polyolefin oligomer. These may have a reactive double bond, react with other components in the adhesive composition with a functional group, or may not react with other components.

<Cross-linking agent>

The resin composition for a pressure-sensitive adhesive of the present invention may further contain a crosslinking agent, if necessary. When the resin composition for a pressure-sensitive adhesive contains a crosslinking agent, the crosslinking density of the pressure-sensitive adhesive layer can be increased by curing (crosslinking) the resin composition for a pressure-sensitive adhesive. Thereby, the strength and the holding force of the adhesive layer tend to be more excellent. In addition, depending on the application, it is not necessary to include a crosslinking agent. Further, when the copolymer (A) has a self-crosslinking property, for example, both of a hydroxyl group and an isocyanato group, sufficient strength and retention force can be obtained without containing a crosslinking agent.

Examples of the cross-linking agent include isocyanate-based, epoxy-based, metal chelating-based, and photo-curing systems, melamine-based, aziridine-based and the like. Any of these crosslinking agents may be used singly or two or more kinds thereof may be used in combination.

Examples of the isocyanate crosslinking agent include aromatic polyisocyanates such as xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate and tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogen of the aromatic polyisocyanate Aliphatic or alicyclic polyisocyanates such as adducts, dimers or trimesters of these polyisocyanates, adducts containing polyols such as polyisocyanates and trimethylolpropane, and the like. Any one of them may be used alone, or two or more of them may be used in combination.

Examples of the epoxy crosslinking agent include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A type epoxy resin, N, N, N ', N (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidyl aniline, N, N-diglycidyl Toluidine, and the like.

Examples of the metal chelate-based crosslinking agent include compounds in which a polyvalent metal is covalently bonded or coordinated to an organic compound. Examples of the polyvalent metal include aluminum, nickel, chromium, copper, iron, tin, titanium, zinc, cobalt, manganese and zirconium. Examples of the organic compound include an organic compound having an oxygen atom such as a ketone compound such as acetylacetone, an alkyl ester, an alcohol compound, a carboxylic acid compound, and an ether compound.

The photopolymerizable crosslinking agent is a compound which undergoes a crosslinking reaction under the action of a photopolymerization initiator or the like upon irradiation with active energy rays such as ultraviolet rays.

Examples of the cross-linking agent of such a species include a polymerizable polyfunctional compound having two or more radically polymerizable groups; A polyfunctional organic resin having at least two functional groups selected from the group consisting of an isocyanate group, an epoxy group, a melamine group, a glycol group, a siloxane group and an amino group; And an organometallic compound having a metal complex. Examples of the metal in the metal complex include zinc, aluminum, sodium, zirconium, calcium and the like.

Examples of the radically polymerizable group in the polymerizable polyfunctional compound include the same ones as described above, and a (meth) acryloyl group is preferable. That is, the polymerizable polyfunctional compound is preferably a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups.

Examples of the polyfunctional (meth) acrylate include triethylene glycol diacrylate, polyalkylene glycol diacrylate, bisphenol A-EO / PO modified diacrylate, alkoxylated hexanediol diacrylate, polyisobutylene Acrylate, alkoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, alkoxylated pentaerythritol triacrylate, alkoxylated pentaerythritol tetraacrylate, alkoxylated dipentaerythritol pentaacrylate, caprolactone modified Dipentaerythritol pentaacrylate, and caprolactone-modified dipentaerythritol hexaacrylate. Any of these polyfunctional (meth) acrylates may be used singly or in combination of two or more.

&Lt; Reaction Initiator &

The resin composition for a pressure-sensitive adhesive of the present invention may further contain a reaction initiator if necessary.

The reaction initiator is a compound which generates a radical by irradiation or heating of an active energy ray (ultraviolet ray or the like).

As the reaction initiator, for example, a photopolymerization initiator, a thermal polymerization initiator and the like can be given.

Examples of the photopolymerization initiator include a compound which is decomposed by irradiation with an active energy ray to generate a radical and a compound which generates radicals by drawing hydrogen from the constituent components in the compound by irradiation with active energy rays.

The photopolymerization initiator is not particularly limited and a known photopolymerization initiator can be suitably used, and examples thereof include benzophenone, 2-methylbenzophenone, 4-methylbenzophenone, 2,2-dimethoxy-1,2-diphenylethane Phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-methyl- 2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2- (dimethylamino) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1, 2-octanedione 1- [4- (phenylthio) -2- (o-benzoyloxime)], ethanone 1- [9- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime). Any one of these photopolymerization initiators may be used alone, or two or more of them may be used in combination.

<Filler>

The resin composition for a pressure-sensitive adhesive of the present invention may further contain a filler as required.

The filler is used, for example, to impart heat resistance, thermal conductivity, flame retardancy, electrical conductivity, and the like. Examples of the filler include inorganic fillers such as metal powder such as zinc oxide powder and titanium oxide powder, carbon black such as acetylene black, talc, glass powder, silica powder, conductive particles and glass powder; Organic fillers such as polyethylene powder, polyester powder, polyamide powder, fluorine resin powder, polyvinyl chloride powder, epoxy resin powder and silicone resin powder; And the like. Any one of these fillers may be used alone, or two or more of these fillers may be used in combination.

<Organic solvents>

The resin composition for a pressure-sensitive adhesive of the present invention may contain an organic solvent for improving the coatability, the film formability and the like, if necessary.

The organic solvent is not particularly limited as long as it can dissolve the copolymer (A), and examples thereof include hydrocarbon solvents such as heptane, cyclohexane, toluene, xylene, octane and mineral spirit; Ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; Alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, s-butanol and isobutanol; Ether solvents such as dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and propylene glycol monopropyl ether; And aromatic petroleum solvents such as Swazol 310, Swazol 1000, and Swazol 1500, which are similar to Cosmo sake. Any of these organic solvents may be used singly or in combination of two or more kinds.

When the resin composition for a pressure-sensitive adhesive is a resin composition for an active energy ray-curable pressure-sensitive adhesive, it is preferable that the resin composition for a pressure-sensitive adhesive contains substantially no organic solvent. The fact that substantially no organic solvent is contained means that the content of the organic solvent is 1% by mass or less based on the total mass of the resin composition for a pressure-sensitive adhesive. The content of the organic solvent may be 0 mass%. The content of the organic solvent can be measured by gas chromatography.

<Other additives>

The resin composition for a pressure-sensitive adhesive of the present invention may suitably contain various additives such as a reaction catalyst, a tackifier resin, an antioxidant, a photostabilizer, a metal deactivation agent, an anti-aging agent, a hygroscopic agent, a rust inhibitor and a hydrolysis inhibitor.

Examples of the reaction catalyst include a tertiary amine compound, a quaternary ammonium compound, and a tin laurate compound.

Examples of the antioxidant include phenol-based, phosphorus-based, hydroxylamine-based, and sulfur-based ones. Among them, a phenol-based or phosphoric-based antioxidant is preferred because the coloration of the resin after heating is low. These may be used alone or in combination of several kinds. The content of the antioxidant is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the copolymer (A).

The resin composition for a pressure-sensitive adhesive of the present invention can be produced, for example, by preparing the above-mentioned copolymer (A), adding other components (polymerizable monofunctional compound, crosslinking agent, photopolymerization initiator, etc.) to the copolymer (A) .

The composition of the resin composition for a pressure-sensitive adhesive may be suitably set in accordance with the use of the resin composition for a pressure-sensitive adhesive, the mode of use, and the like.

<Preferred Embodiment>

As preferred embodiments of the resin composition for a pressure-sensitive adhesive of the present invention, the following resin compositions (1) to (3) for a pressure-sensitive adhesive may be mentioned.

(Resin composition (1) for pressure-sensitive adhesive)

The resin composition (1) for a pressure-sensitive adhesive contains at least a copolymer (A), a polymerizable monofunctional compound having one radically polymerizable group, a polymerizable polyfunctional compound having two or more radically polymerizable groups and a photopolymerization initiator And is a liquid resin composition for a pressure-sensitive adhesive.

The resin composition (1) for a pressure-sensitive adhesive is an active energy ray-curable type.

"Liquid phase" means liquid phase at 25 ° C. The viscosity of the resin composition (1) for a liquid pressure-sensitive adhesive measured by a B-type viscometer at 25 占 폚 is preferably 1,000 to 800,000 mPa 占 퐏.

The resin composition (1) for a pressure-sensitive adhesive preferably contains substantially no organic solvent.

The resin composition (1) for a pressure-sensitive adhesive may further contain a filler, an oligomer component, other additives and the like as necessary.

The pressure-sensitive adhesive resin composition (1) can be used, for example, as LOCA.

The content of the copolymer (A) in the pressure-sensitive adhesive resin composition (1) is preferably from 10 to 80 mass%, more preferably from 15 to 80 mass%, based on the total mass of the copolymer (A) and the polymerizable monofunctional compound (100 mass% And more preferably 70% by mass. If the lower limit is not lower than the upper limit, the viscosity at the time of coating or filling at the time of forming the pressure-sensitive adhesive layer becomes an appropriate value, and workability is improved.

The content of the polymerizable polyfunctional compound in the pressure-sensitive adhesive resin composition (1) is preferably from 0.1 to 50 parts by mass, more preferably from 0.5 to 20 parts by mass, per 100 parts by mass of the total of the copolymer (A) and the polymerizable monofunctional compound More preferable. If the lower limit is not lower than the upper limit, the viscosity at the time of coating or filling at the time of forming the pressure-sensitive adhesive layer becomes an appropriate value, and workability is improved.

The content of the photopolymerization initiator in the pressure-sensitive adhesive resin composition (1) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the copolymer (A). If the lower limit value is not more than the upper limit value, the holding strength and durability of the pressure-sensitive adhesive layer are improved.

(Resin composition (2) for pressure-sensitive adhesive)

The resin composition (2) for a pressure-sensitive adhesive is a resin composition for a hot-melt type pressure-sensitive adhesive comprising the copolymer (A).

The resin composition (2) for a pressure-sensitive adhesive is solid at 25 占 폚.

The resin composition (2) for a pressure-sensitive adhesive contains substantially no organic solvent.

The resin composition (2) for a pressure-sensitive adhesive may further contain a polymerizable monofunctional compound, a crosslinking agent, a reaction initiator, a filler, an oligomer component, other additives and the like, if necessary.

The resin composition (2) for a pressure-sensitive adhesive preferably includes a cross-linking agent. Thus, the pressure-sensitive adhesive layer or pressure-sensitive adhesive sheet formed from the resin composition for a pressure-sensitive adhesive (2) can be cured (crosslinked).

It is preferable that the resin composition (2) for a pressure-sensitive adhesive is an active energy ray-curable type comprising a polymerizable polyfunctional compound having two or more radically polymerizable groups as a crosslinking agent and a photopolymerization initiator as a reaction initiator.

The resin composition (2) for a pressure-sensitive adhesive can be molded, for example, on a transparent double-sided pressure-sensitive adhesive sheet, and crosslinked as necessary to be used as OCA.

The content of the copolymer (A) in the pressure-sensitive adhesive resin composition (2) is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 100 mass% with respect to the total mass of the resin composition for a pressure-sensitive adhesive. When the lower limit is not more than the upper limit, the durability of the pressure-sensitive adhesive layer is improved.

When the pressure-sensitive adhesive resin composition (2) contains a crosslinking agent, the content of the crosslinking agent in the resin composition (2) for a pressure-sensitive adhesive can be appropriately set depending on the type of the crosslinking agent. For example, when the crosslinking agent is the polymerizable polyfunctional compound, the content of the polymerizable polyfunctional compound is preferably 1 to 20 parts by mass, more preferably 3 to 10 parts by mass, per 100 parts by mass of the copolymer (A) . When the lower limit is not more than the upper limit, the durability of the pressure-sensitive adhesive layer is improved.

When the pressure-sensitive adhesive resin composition (2) contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the copolymer (A). When the lower limit is not more than the upper limit, the durability of the pressure-sensitive adhesive layer is improved.

(Resin composition (3) for pressure-sensitive adhesive)

The resin composition (3) for a pressure-sensitive adhesive is a liquid resin composition for a pressure-sensitive adhesive comprising a copolymer (A) and an organic solvent.

The viscosity of the liquid composition for a pressure-sensitive adhesive (3) measured at 25 캜 by a B-type viscometer is preferably from 10 to 800,000 mPa · s, more preferably from 100 to 10,000 mPa · s, and from 200 to 7,000 mPa · s More preferably from 200 to 5,000 mPa · s, and most preferably from 500 to 3500 mPa · s. When the lower limit is not more than the upper limit, the coating property and workability at the time of coating the resin composition for a liquid pressure sensitive adhesive are improved.

The resin composition (3) for a pressure-sensitive adhesive may further contain, if necessary, a polymerizable monofunctional compound, a crosslinking agent, a reaction initiator, a filler, an oligomer component and other additives.

The resin composition (3) for a pressure-sensitive adhesive preferably contains a crosslinking agent. As a result, the pressure-sensitive adhesive layer or the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive resin composition (3) can be cured (crosslinked).

The resin composition (3) for a pressure-sensitive adhesive is a crosslinking agent which is obtained by reacting a polymerizable polyfunctional compound having two or more radically polymerizable groups, an active energy ray-curable type containing a photopolymerization initiator as a reaction initiator or a functional group contained in the copolymer A It is preferably a thermosetting type compound.

The resin composition (3) for a pressure-sensitive adhesive is obtained, for example, by applying a resin composition (3) for a pressure-sensitive adhesive on a releasable substrate and drying the same to form a transparent double-sided pressure-sensitive adhesive sheet, It can be used as a pressure-sensitive adhesive.

The content of the copolymer (A) in the pressure-sensitive adhesive resin composition (3) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass based on the solid content of the resin composition for a pressure-sensitive adhesive. When the lower limit is not more than the upper limit, the durability of the pressure-sensitive adhesive layer is improved.

The solid content of the resin composition for a pressure-sensitive adhesive is a residue excluding the organic solvent from the resin composition (3) for a pressure-sensitive adhesive.

The solid content concentration of the resin composition for a pressure-sensitive adhesive may be appropriately set in consideration of the viscosity of the resin composition for a pressure-sensitive adhesive, and may be, for example, 10 to 90% by mass. The amount of the organic solvent in the pressure-sensitive adhesive resin composition (3) is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less from the viewpoints of productivity and environmental load reduction.

When the pressure-sensitive adhesive resin composition (3) contains a crosslinking agent, the content of the crosslinking agent in the resin composition (3) for a pressure-sensitive adhesive can be suitably set in accordance with the type of the crosslinking agent. For example, when the crosslinking agent is the polymerizable polyfunctional compound, the content of the polymerizable polyfunctional compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the copolymer (A) . When the lower limit is not more than the upper limit, the durability of the pressure-sensitive adhesive layer is improved.

When the crosslinking agent is the thermosetting type, examples of the crosslinking agent include thermosetting crosslinking agents such as an isocyanate type, an epoxy type, a metal chelate type, and a photopolymerization type, such as melamine type and aziridine type. Specific examples of crosslinking agents such as isocyanate-based, epoxy-based, metal chelating-based, and carbodiimide-based ones include the same ones as described above. These crosslinking agents may be used singly or in combination of two or more kinds.

When the crosslinking agent is the thermosetting type, the copolymer (A) preferably contains a structural unit having a functional group capable of reacting with the crosslinking agent. Examples of the functional group capable of reacting with the crosslinking agent include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, an amino group, an amide group and a thiol group.

When the crosslinking agent is the thermosetting type, the content of the thermosetting crosslinking agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the copolymer (A). When the lower limit is not more than the upper limit, the time for which the composition for pressure-sensitive adhesive is used is good or the durability of the pressure-sensitive adhesive layer is improved.

When the pressure-sensitive adhesive resin composition (3) contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the copolymer (A). When the lower limit is not more than the upper limit, the durability of the pressure-sensitive adhesive layer is improved.

<Applications>

The resin composition for a pressure-sensitive adhesive of the present invention can be used for bonding members together.

At the time of bonding, the resin composition for a pressure-sensitive adhesive may be preliminarily formed into a sheet form or applied to form a pressure-sensitive adhesive sheet, or may be disposed directly between members without being formed into a sheet-like form.

The adhesive sheet will be described later in detail.

The member to be bonded by using the resin composition for a pressure-sensitive adhesive of the present invention is not particularly limited. For example, it can be used for joining a window-attaching film for automobiles, architectural use, etc., and for joining labels in labeling.

When the resin composition for a pressure-sensitive adhesive is transparent, it can be processed into a transparent double-sided pressure-sensitive adhesive sheet, and can be used as OCA for joining various panels in a display such as a liquid crystal panel or joining transparent plates such as glass. When the resin composition for a pressure-sensitive adhesive is transparent and liquid, it can be used as such as LOCA as it is.

"Transparent" means that a pressure-sensitive adhesive sheet adjusted to a thickness of 150 μm has a haze value of 10 or less when measured by a method according to JIS K7361.

Examples of the material of the member include glass, polyethylene terephthalate, polycarbonate, polycarbonate, acrylic resin, polyvinyl alcohol, silicone resin, and the like.

An example of a method of joining members using the resin composition for a pressure-sensitive adhesive of the above (1) is described below.

First, a resin composition for a pressure-sensitive adhesive of the above-mentioned (1) is applied to the surface of a first member to form a pressure-sensitive adhesive layer, a second member is laminated thereon, and cured as required. Thereby, a laminate in which the first member and the second member are bonded together via the adhesive layer is obtained.

The application of the resin composition for a pressure-sensitive adhesive of the above (1) can be carried out by a known wet coating method such as slit coating and spin coating. Alternatively, a method may be employed in which a resin composition for a pressure-sensitive adhesive is filled between a first member and a second member by applying a predetermined amount of a resin composition for a pressure-sensitive adhesive to bond the second member.

The application amount of the resin composition for a pressure-sensitive adhesive of the above (1) is set according to the thickness of the pressure-sensitive adhesive layer to be formed. The thickness of the adhesion layer can be suitably set in accordance with the application, and is not particularly limited, but is typically about 10 to 500 mu m.

When the resin composition for a pressure-sensitive adhesive is curable, the pressure-sensitive adhesive layer (resin composition for a pressure-sensitive adhesive) may be cured before or after the second member is laminated.

The curing method of the adhesive layer is not particularly limited. For example, when the resin composition for a pressure-sensitive adhesive contains a polyfunctional (meth) acrylate as a crosslinking agent and a photopolymerization initiator, the pressure-sensitive adhesive layer can be cured (photo-cured) by irradiation with active energy rays such as ultraviolet rays. When the copolymer (A) has a reactive group such as a hydroxyl group and the resin composition for a pressure-sensitive adhesive contains a crosslinking agent (isocyanate-based or the like) capable of chemically bonding with the reactive group by heat, the adhesive layer is cured ).

When the adhesive layer is photo-cured, ultraviolet rays are preferable as the active energy ray from the viewpoint of versatility. Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp.

When the adhesive layer is thermally cured, the heating means can be carried out using a known heating means, for example, a drying furnace such as a hot air furnace, an electric furnace or an infrared induction heating furnace. The heating temperature is not particularly limited, but is preferably about 50 to 180 占 폚. The heating time is not particularly limited, but is preferably about 10 seconds to 60 minutes.

Preheating, air blowing, and the like may be performed under heating conditions in which the resin composition for a pressure-sensitive adhesive is not substantially cured in order to prevent the occurrence of defects before thermal curing. The preliminary heating can be carried out at a temperature of, for example, about 30 to 100 DEG C for about 30 seconds to 15 minutes. Air blowing can usually be performed by spraying heated air at a temperature of about 30 to 100 DEG C for about 30 seconds to about 15 minutes on the coated surface.

After the thermal curing, curing may be performed. The curing condition may be, for example, about 0 to 60 DEG C for about 1 to 10 days.

In the resin composition for a pressure-sensitive adhesive of the present invention, a pressure-sensitive adhesive layer having a sufficient retentivity and an appropriate range of adhesion and a low substrate stain due to residual adhesive can be formed because the copolymer (A) is included.

[Adhesive sheet]

The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet using the above-mentioned pressure-sensitive adhesive resin composition. That is, it is a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the resin composition for a pressure-sensitive adhesive.

When the resin composition for a pressure-sensitive adhesive is curable, the pressure-sensitive adhesive sheet of the present invention may contain the resin composition for a pressure-sensitive adhesive, or may include a cured product of the resin composition for a pressure-sensitive adhesive. From the viewpoint of handling property of the pressure-sensitive adhesive sheet, it is preferable to include a cured product of the pressure-sensitive adhesive resin composition.

The pressure sensitive adhesive sheet of the present invention may be a transparent double side pressure sensitive adhesive sheet.

The thickness of the pressure-sensitive adhesive sheet of the present invention can be suitably set in accordance with the application, and is not particularly limited, but is typically about 10 to 500 mu m.

The pressure sensitive adhesive sheet of the present invention may be a pressure sensitive adhesive sheet having a releasable base material laminated on one side or both sides of the pressure sensitive adhesive sheet.

The pressure-sensitive adhesive sheet of the present invention can be produced by molding the above-mentioned pressure-sensitive adhesive resin composition into a sheet and curing it if necessary.

The molding of the resin composition for a pressure-sensitive adhesive can be carried out by a known method. For example, when the resin composition for a pressure-sensitive adhesive of the present invention is in a solid form (for example, in the case of the resin composition (2) for a pressure-sensitive adhesive), a resin composition for an adhesive is disposed between a pair of peelable substrates, And a method in which the resin composition for a pressure-sensitive adhesive is heated from both sides of the peelable base material to form a sheet-like composition. When the resin composition for a pressure-sensitive adhesive of the present invention is a liquid (for example, in the case of the resin composition (1) or (3) for a pressure-sensitive adhesive), a resin composition for an adhesive is applied to a releasable substrate, , And the like.

The curing can be performed in the same manner as the curing of the adhesive layer.

The pressure-sensitive adhesive sheet of the present invention can be used for bonding members such as the above-mentioned pressure-sensitive adhesive resin composition.

For example, an adhesive sheet is disposed on the surface of the first member, a second member is laminated on the adhesive sheet, and is cured as required. Thereby, a laminate in which the first member and the second member are bonded together via the adhesive sheet is obtained.

The pressure-sensitive adhesive sheet of the present invention has a sufficient holding power and an appropriate range of adhesive force in that the pressure-sensitive adhesive sheet uses the above-mentioned pressure-sensitive adhesive resin composition. Furthermore, the stain resistance of the substrate due to the residual adhesive is low.

[Protective Sheet]

The protective sheet of the present invention is a protective sheet using the above resin composition for a pressure-sensitive adhesive. That is, it is a protective sheet comprising an adhesive layer formed from the resin composition for a pressure-sensitive adhesive.

When the resin composition for a pressure-sensitive adhesive is curable, the protective sheet of the present invention may contain the resin composition for a pressure-sensitive adhesive, or may contain a cured product of the resin composition for a pressure-sensitive adhesive. From the viewpoint of handleability of the protective sheet, it is preferable to include a cured product of the resin composition for a pressure-sensitive adhesive.

The thickness of the protective sheet of the present invention can be suitably set according to the application, and is not particularly limited, but is typically about 5 to 100 mu m.

The protective sheet of the present invention may be a protective sheet provided with a peelable base material laminated on one side or both sides of a protective sheet.

The protective sheet of the present invention can be produced in the same manner as the above-mentioned adhesive sheet.

The protective sheet of the present invention is used for protecting the substrate surface. Typically bonded to the substrate surface, and then peeled from the substrate surface when protection is no longer required.

The substrate to be protected by the protective sheet of the present invention is not particularly limited and includes, for example, a polarizer used for a touch panel display, an optical member such as a front face plate, a component such as an automobile, a motorcycle, And the like.

Since the protective sheet of the present invention uses the resin composition for a pressure-sensitive adhesive, peeling after bonding to the surface of the substrate is difficult to occur because the protective sheet has sufficient holding power and adhesive strength in an appropriate range, When protection is no longer required, it can be easily peeled from the substrate surface.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of the present invention. In the following examples, &quot; part &quot; represents &quot; part by mass &quot;.

The measuring method used in each example is shown below.

<Measurement method>

(Number average molecular weight of macromonomer)

The number average molecular weight (Mn) of the macromonomer was measured using a gel permeation chromatography (GPC) apparatus (HLC-8320, manufactured by Tosoh Corporation). The above solution was injected into the above apparatus equipped with a toluene column (TSKgel SuperHZM-M 占 HZM-M 占 HZ2000, TSKguardcolumn SuperHZ-L), and the flow rate : 0.35 mL / min, eluent: THF (stabilizer: butylhydroxytoluene (BHT)), column temperature: 40 DEG C, and the number average molecular weight was calculated in terms of standard polystyrene.

(Weight average molecular weight of the copolymer)

The weight average molecular weight (Mw) of the copolymer was measured using a GPC apparatus (HLC-8120, manufactured by Tosoh Corporation). A THF solution of 0.3 mass% of the copolymer was prepared and 20 占 퐇 of the solution was injected into the apparatus equipped with a column made by Doso (TSKgel SuperHM-H 占 4, TSKguardcolumn SuperH-H). The flow rate was 0.6 ml / THF (stabilizer BHT), column temperature: 40 DEG C, and the weight average molecular weight (Mw) was calculated in terms of standard polystyrene.

(The viscosity of 50% ethyl acetate solution of the copolymer was measured)

The 50% ethyl acetate solution viscosity of the copolymer was determined by measuring the ethyl acetate solution having the polymer content of the copolymer of 50% at 25 캜 by the B type rotational viscosity (B8H type).

(Incineration X-ray Scattering Measurement of Copolymer (SAXS))

The incineration X-ray scattering measurement was carried out at BL03XU (Frontier Software Development Laboratory, Beamline, SPring-8, large-scale synchrotron facility).

The copolymer solution obtained in each example was coated on a 50 占 퐉 peelable PET film with a 500 占 퐉 applicator and dried at 90 占 폚 for 90 minutes to form a copolymer layer. A 50 占 퐉 peelable PET film was bonded thereon, - Adhesive layer-A laminated sheet constituted of a peelable PET film was obtained. The PET indicates the polyethylene terephthalate, the "peeling" in front of the PET film indicates the peeling treatment, and the numerical value (탆) in front of the PET film indicates the thickness of the PET film (hereinafter the same).

One of the peelable PET films of the laminated sheet was peeled off to expose the copolymer layer and bonded to the sample jig. Thereafter, the remaining peelable PET film was peeled off, and only the copolymer layer was placed on the sample jig. Using this copolymer layer as a sample, a two-dimensional scattering image of a sample was obtained in the following procedure.

The X-ray beam shape was adjusted to 120 mu m in length and 120 mu m in width. The X-ray wavelength was 1 angstrom, and the detector was a CCD (Hamamatsu Photonics V7739P + ORCA R2). The length of the camera was set to about 4 m, and correction was performed using a standard sample (collagen). The type, thickness, and exposure time of the attenuator (attenuation plate) were adjusted so that the detector was not damaged by the strong X-ray, and then the sample was irradiated with X-rays to obtain a two-dimensional scattering image of the sample.

The background was corrected from the two-dimensional scattering image of the sample obtained in the above procedure. More specifically, a two-dimensional scattering image of the background obtained by performing the same operation as the above procedure in the absence of a sample is obtained and the two-dimensional scattering image of the background is subtracted from the two-dimensional scattering image of the sample using the image processing software (Image-J) , And a two - dimensional scattering image for analysis was obtained. In the two dimensional scattering image for analysis, ring phase scattering was confirmed.

Then, the two-dimensional scattering image for analysis was converted into a one-dimensional scattering spectrum. Specifically, a two-dimensional scattering image for analysis was read by an X-ray data processing software (Fit2d) and integrated over all directions to obtain a one-dimensional scattering spectrum having a horizontal axis as q [nm ^-1 ] and a vertical axis as a scattering intensity. The range of q (the region to be analyzed) was 0.04 to 0.4. A one-dimensional scattering spectrum showed peaks between q = 0.2 and 0.4.

From the obtained one-dimensional scattering profile, the half-width X of the one-dimensional scattering peak and the peak position Y of the one-dimensional scattering profile were determined.

In one-dimensional scattering profile, there is a case where the scattering intensity increases toward the origin and a scattering intensity decreases toward the origin after passing through the inflection point near q = 0.1 by taking a minimum value near q = 0.1 and increasing the intensity toward the origin. When the minimum value is taken around q = 0.1 and the scattering intensity increases toward the origin, an area larger than the minimum value q is taken as an analysis object. When the scattering intensity decreases toward the origin after passing through the inflection point near q = 0.1, the region larger than the inflection point q is considered as the analysis target. Subsequently, as the baseline correction, the minimum value of the scattering intensity of the region to be analyzed was obtained, and the minimum value was subtracted over the entire region to perform baseline correction. The resulting one-dimensional scattering profile was fitted with a Gaussian function and a Lorentz function. The half width (half width) and the peak position of the obtained composite function were X and Y, respectively. Waveform separation software (Fityk) was used for fitting.

&Lt; Synthesis Example 1 &

(Preparation of Dispersant 1)

900 parts of deionized water, 60 parts of 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate and 12 parts of methyl methacrylate (MMA) were placed in a polymerization apparatus equipped with a stirrer, a cooling tube, a thermometer and a nitrogen gas introducing tube And the temperature was raised to 50 캜 while the inside of the polymerization apparatus was replaced with nitrogen. 0.08 part of 2,2'-azobis (2-methylpropionamidine) dihydrochloride as a polymerization initiator was added thereto, and the temperature was further raised to 60 ° C. After the temperature was elevated, MMA was continuously added dropwise at a rate of 0.24 parts / min for 75 minutes using a dropping pump.

The reaction solution was maintained at 60 캜 for 6 hours and then cooled to room temperature to obtain a dispersant 1 having a solid content of 10% by mass as a transparent aqueous solution.

(Manufactured by chain transfer agent 1)

1.00 g of cobalt (II) acetate tetrahydrate, 1.93 g of diphenylgoldoxime and 80 mL of deoxygenated diethyl ether in advance by nitrogen bubbling were charged into a reactor equipped with a stirrer under nitrogen atmosphere, and the mixture was stirred at room temperature for 30 minutes Respectively. Subsequently, 10 mL of boron trifluoride diethyl ether complex was added, and the mixture was further stirred for 6 hours. The mixture was filtered, the solid was washed with diethyl ether and vacuum dried for 15 hours to obtain 2.12 g of chain transfer agent 1 which is a reddish brown solid.

(Preparation of macromonomer)

145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of dispersant 1 (solid content 10% by mass) were added to a polymerization apparatus equipped with a stirrer, a cooling tube, a thermometer and a nitrogen gas introducing tube and stirred to prepare a uniform aqueous solution. Subsequently, 100 parts of MMA, 0.0035 parts of chain transfer agent and 100 parts of Peroocta (registered trademark) O (1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, manufactured by Nippon Oil Co., Ltd.) 0.4 part was added to obtain an aqueous suspension.

Subsequently, the inside of the polymerization apparatus was purged with nitrogen, and the temperature was raised to 80 캜 and reacted for 3.5 hours. The temperature was raised to 90 캜 and maintained for 1 hour in order to increase the polymerization rate. Thereafter, the reaction solution was cooled to 40 캜 to obtain an aqueous suspension containing the macromonomer. The aqueous suspension was filtered, the residue remained on the filter was washed with deionized water, dehydrated and dried at 40 占 폚 for 16 hours to obtain macromonomer (a-1). The number average molecular weight of the macromonomer (a-1) was 3,000.

&Lt; Synthesis Example 2 &

Macromonomer (a-2) was obtained in the same manner as in Synthesis Example 1 except that the amount of peroxide O and chain transfer agent 1 was changed as shown in Table 1 in Synthesis Example 1 (Preparation of Macromonomer). The number-average molecular weight of this macromonomer (a-2) was 6,700.

&Lt; Preparation Example 1 &

A four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas inlet was charged with 40 parts of ethyl acetate and 8 parts of isopropyl alcohol (IPA) as an initial charge additive, ) And 5 parts of lauryl (LA) acrylate were placed, and the outside temperature was raised to 85 캜 under nitrogen gas flow. After the outside temperature reached 85 DEG C and the internal temperature was stabilized, a mixture (20 parts) of ethyl acetate, 84.5 parts of LA, 0.5 part of acrylic acid, and 0.13 part of NIPPER BMT-K40 (trade name, benzoyl peroxide) ) Was added dropwise over 4 hours. After the completion of the dropwise addition for 1 hour, a mixture containing 0.5 part of perocta O and 10 parts of ethyl acetate was added over 1 hour. Thereafter, after maintaining for 2 hours, 0.5 part of an antioxidant (product name: "Irganox (registered trademark) 1010" manufactured by BASF) was added and the solid content (the ratio of the amount of monomer introduced into the monomer + solvent) Ethyl acetate was added as required, and then cooled to room temperature to obtain a copolymer solution (A-1).

The half-width X of the one-dimensional scattering peak in the measurement of the incinerated X-ray scattering (SAXS) and the peak position Y of the one-dimensional scattering profile in the copolymer solution (A-1), the weight average molecular weight The solution viscosity is shown in Table 2.

&Lt; Production Examples 2 to 9 &

Except that the initial charging solvent, the initial charging monomer, the solvent (dropping solvent) in the mixture to be dropped after raising the temperature and the monomer (dropping monomer) were changed as shown in Table 2, A-2) to (A-9).

Table 2 shows the weight average molecular weight (Mw) of the copolymer in the copolymer solution obtained in each example, the half width X of the one-dimensional scattering peak X and the peak position Y of the one-dimensional scattering profile in the measurement of incineration X-ray scattering (SAXS).

&Lt; Example 1 >

80 parts of the copolymer solution (A-1) was desolvated to have a solid content of 99% or more, and 60 parts of isodecyl acrylate (IDAA), 60 parts of a crosslinking agent (PETA: Shin Nakamura Kagaku, trade name &quot; NK Ester TMM- (Trade name) &quot; IRGACURE (registered trademark) 184 &quot;, 1-hydroxycyclohexylphenylketone) were mixed to prepare a resin composition for a pressure-sensitive adhesive in a liquid state.

A pressure-sensitive adhesive sheet was prepared by the following procedure for the obtained pressure-sensitive adhesive resin composition, and the pressure-sensitive adhesive sheet was evaluated for adhesive force, holding force, and substrate stain resistance in the following procedure. The results are shown in Table 3.

(Production of pressure-sensitive adhesive sheet)

A resin composition for a pressure-sensitive adhesive was applied onto a peelable polyethylene terephthalate (PET) film by an applicator so that the thickness of the pressure-sensitive adhesive layer became 50 占 퐉, a 50 占 퐉 peelable PET film was bonded to the pressure- To thereby cure the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet having a peelable PET-adhesive layer-peelable PET structure. The peelable PET film means the peeled PET film.

"Survey conditions"

Light source: high pressure mercury lamp, irradiation intensity: 200 mW / cm ² , cumulative light amount: 3000 mJ / cm ² .

(adhesiveness)

One peelable PET film of the pressure-sensitive adhesive sheet was peeled off and a 38 mu m PET film was bonded thereon to obtain a laminate. This laminate was cut into a rectangle having a width of 25 mm and a length of 300 mm and the other release film was peeled to expose the adhesive layer and bonded to the glass plate using a 2 kg hand roller so as to have a bonding surface of 25 mm x 120 mm, The peel strength (N / 25 mm) on the glass plate was measured at a peel angle of 180 ° and a tensile rate of 300 mm / min in accordance with Z 0237 to determine the adhesive strength.

A: Adhesion less than 2N / 25mm.

B: Adhesive strength greater than 2N / 25mm, 3N / 25mm or less.

C: Adhesive strength is greater than 3N / 25mm.

(retention)

One of the peelable PET films of the pressure-sensitive adhesive sheet was peeled off, and instead a 38 탆 PET film was pressed with a 2 kg hand roller to obtain a laminate. This laminate was cut into a rectangle of 25 mm x 100 mm and the other peeling PET film was peeled off. Using a 2 kg hand roller on a stainless steel (SUS) plate of 30 mm x 100 mm, . According to JIS Z 0237, after curing at 40 占 폚 for 30 minutes, a weight of 1 kg was attached to the end of the PET film, and the holding time was measured in a constant temperature layer at 40 占 폚. The retentivity was determined according to the following criteria.

A: The holding time is over 100 minutes.

B: The holding time is more than 60 minutes and less than 100 minutes.

C: The holding time is less than 60 minutes.

(Stain resistance on the substrate)

One peelable PET film of the pressure-sensitive adhesive sheet was peeled off and a 38 mu m PET film was bonded thereon to obtain a laminate. This laminated body was cut into a rectangle having a width of 25 mm and a length of 300 mm and the other side of the release film was peeled to expose the adhesive layer and a 2 kg hand roller was used for an SUS plate of 30 mm x 150 mm so as to have a contact surface of 25 mm x 12 mm And allowed to stand at 60 占 폚 for 2 weeks. Thereafter, the pressure-sensitive adhesive sheet was peeled off under the same conditions as the adhesive strength test, and the SUS surface was visually observed to determine the substrate stain resistance according to the following criteria.

A: There is no residual adhesive.

B: Residual adhesive.

&Lt; Example 2 >

A resin composition for a pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that the copolymer used was changed to that shown in Table 3, and a pressure-sensitive adhesive sheet was prepared to evaluate the adhesive strength, the holding power and the substrate stain resistance.

&Lt; Example 3 >

A resin composition for a pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that the copolymer used was changed to that shown in Table 3, and a pressure-sensitive adhesive sheet was produced in the following manner. , And the substrate stain resistance was evaluated.

(Production of pressure-sensitive adhesive sheet)

A resin composition for a pressure-sensitive adhesive was sandwiched between peeling PET films, and an adhesive layer having a thickness of 100 占 퐉 was formed by hot pressing at 100 占 폚 to obtain a pressure-sensitive adhesive sheet having a peeling PET-adhesive layer- Sensitive adhesive layer was irradiated with ultraviolet rays (UV) to cure the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet having a PET-adhesive layer-peeling PET structure.

"Survey conditions"

Light source: high pressure mercury lamp, irradiation intensity: 200 mW / cm ² , cumulative light amount: 3000 mJ / cm ² .

<Example 4>

200 parts of the copolymer solution (A-3) and 0.24 parts of polyisocyanate ("Coronate L", product of Tohgo Co., Ltd., trade name) (PIC) were mixed to prepare a resin composition for a pressure-sensitive adhesive.

A pressure-sensitive adhesive sheet was prepared by the following procedure for the obtained pressure-sensitive adhesive resin composition, and the pressure-sensitive adhesive sheet was evaluated for adhesion, retention, and substrate stain resistance in the same manner as in Example 1.

(Production of pressure-sensitive adhesive sheet)

A resin composition for a pressure-sensitive adhesive was coated on a peelable PET film with an applicator so that the thickness of the pressure-sensitive adhesive layer became 20 占 퐉 and heated at 120 占 폚 for 1 hour to cure the pressure-sensitive adhesive layer. C for 3 days to obtain a pressure-sensitive adhesive sheet having a release PET film-pressure-sensitive adhesive layer-release PET film.

&Lt; Examples 5 to 9, Comparative Examples 1 and 2 >

A resin composition for a pressure-sensitive adhesive was prepared in the same manner as in Example 6 except that the kind of the copolymer solution was changed as shown in Table 3, and a pressure-sensitive adhesive sheet was prepared to evaluate the adhesive strength, the holding power and the substrate stain resistance. The results are shown in Table 3.

The meanings of the abbreviations in the table are as follows.

MMA: Methyl methacrylate.

2-EHA: 2-ethylhexyl acrylate.

LA: Lauryl acrylate.

IDAA: Isodecyl acrylate.

AA: Acrylic acid.

2-HEA: 2-hydroxyethyl acrylate.

IPA: Isopropyl alcohol.

PETA: pentaerythritol triacrylate (Shin-Nakamura Kagaku, trade name &quot; NK Ester TMM-3L &quot;).

Irg 184: IRGACURE 184 (trade name, product of BASF).

PIC: polyisocyanate (&quot; Coronate L &quot;

Al (acac) ₃ : Aluminum trisacetylacetonate.

The pressure-sensitive adhesive layers of Examples 1 to 9 had adequate adhesive force and sufficient holding power, and were low in substrate staining due to residual adhesive.

The adhesive layer of Comparative Example 1 using a copolymer having a half value width X of more than 0.12 was too high in adhesive strength and thus inferior in releasability.

The adhesive layer of Comparative Example 2 using a copolymer having no one-dimensional scattering peak in the measurement of incineration X-ray scattering (SAXS) and having no half width X did not have a holding power. In addition, substrate contamination due to residual adhesive was observed. It is considered that there was no one-dimensional scattering peak because it was not phase-separated.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet which can form a pressure-sensitive adhesive layer having a sufficient holding power and an appropriate range of adhesive force and a low substrate stain resistance due to residual pressure-sensitive adhesive.

Claims (9)

The present invention relates to a resin composition for a point adhesive comprising a macromonomer (a) and a (meth) acrylic copolymer (A) having a constituent unit derived from a macromonomer (a) and a constituent unit derived from a vinyl monomer (b) , At least two constitutional units represented by the formula (a ') and at least two constitutional units represented by the following formula (1)

Wherein the vinyl monomer (b) comprises an alkyl (meth) acrylate (b1) having an alkyl group having a carbon number of 8 or more, and the half-value of the first peak measured by the incinerating X-ray scattering measurement of the (meth) And the width X satisfies the following formula (i).
0 &lt; (i)
(Wherein R ¹ represents a hydrogen atom, a methyl group or CH ₂ OH, and R ² represents OR ³ , a halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ , NHCOR ⁸ or R ⁹ ,
R ³ to R ⁸ are each independently a hydrogen atom, an alkyl group having an unsubstituted or substituted group, an alicyclic group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, a heteroaryl having an unsubstituted or substituted group A nonaromatic heterocyclic group having an unsubstituted or substituted group, an aralkyl group having an unsubstituted or substituted group, an alkaryl group having an unsubstituted or substituted group, an organosilyl group having an unsubstituted or substituted group, (Poly) organosiloxane group having a substituent, and the substituents in these groups are each an alkyl group, an aryl group, a heteroaryl group, a nonaromatic heterocyclic group, an aralkyl group, an alkaryl group, a carboxylic acid group (COOH) carboxylic acid ester group, an epoxy group, a hydroxy group, an alkoxy group, a primary amino group, secondary amino group, tertiary amino group, isocyanic Ana earthenware, a sulfonic acid group (SO ₃ H) and halogen atoms made Which is at least one member selected from the group, R ⁹ denotes a heterocyclic non-aromatic group having a heteroaryl group, or unsubstituted or substituent having an aryl group, unsubstituted or substituted with a or a substituent unsubstituted , The substituents in these groups are each an alkyl group, an aryl group, a heteroaryl group, a nonaromatic heterocyclic group, an aralkyl group, an alkaryl group, a carboxylic acid group, a carboxylic acid ester group, an epoxy group, a hydroxy group, , A secondary amino group, a tertiary amino group, an isocyanato group, a sulfonic acid group, an alkyl group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, an olefin group having an unsubstituted or substituted group and a halogen atom . &Lt; / RTI &gt; R represents a hydrogen atom, an alkyl group having an unsubstituted or substituted group, an alicyclic group having an unsubstituted or substituted group, an aryl group having an unsubstituted or substituted group, a heteroaryl group having an unsubstituted or substituted group, , An unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, an unsubstituted or substituted organosilyl group, or an unsubstituted or substituted aralkyl group having an unsubstituted or substituted Poly) organosiloxane group, Q represents a main chain portion containing two or more structural units (a '), and Z represents a terminal group. The resin composition for a pressure-sensitive adhesive according to claim 1, wherein the (meth) acrylic copolymer (A) has a weight average molecular weight of 1,000 to 1,000,000. The pressure-sensitive adhesive resin composition according to claim 1 or 2, wherein the content of the structural unit derived from the macromonomer (a) is 3 to 60 mass% with respect to the total mass of the total structural units. The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the macromonomer (a) has a number average molecular weight of 100 or more and 100,000 or less. The pressure-sensitive adhesive resin composition according to any one of claims 1 to 4, wherein the (meth) acrylic copolymer (A) satisfies the condition of the formula (ii).
0.1? X / Y? (ii)
(X represents the half-width of the first-order peak measured by the incineration X-ray scattering measurement and the peak position Y of the one-dimensional scattering profile) The pressure-sensitive adhesive resin composition according to any one of claims 1 to 5, wherein the polymer TgB obtained by polymerizing Tga of the macromonomer (a) and the vinyl monomer (b) satisfies the relationship of the formula (4).
Tga-TgB> 0 ℃ ... (4) The composition according to any one of claims 1 to 6, wherein the solubility parameter 隆 a of the constitutional unit derived from the macromonomer (a) and the solubility parameter 隆 b of the constitutional unit derived from the vinyl monomer (b) satisfy the relationship of the formula (5) By weight.
δa-δb> 0 ... (5) The pressure-sensitive adhesive composition for a pressure-sensitive adhesive according to any one of claims 1 to 7, wherein a solution viscosity of the (meth) acrylic copolymer (A) in a 50% ethyl acetate solution is 10 to 800,000 mPa · s. A pressure-sensitive adhesive sheet using the resin composition for a pressure-sensitive adhesive according to any one of claims 1 to 8.