TWI739965B - Resin composition for adhesive and adhesive sheet - Google Patents

Abstract

The resin composition for the adhesive including a (meth) acrylic copolymer (A) having a constituent unit derived from a macromonomer (a) and a constituent unit derived from a vinyl monomer (b), and the macromonomer (a) is represented by the following formula (1) with two or more constitutional units represented by the following formula (a').

wherein the vinyl monomer (b) is an alkyl (meth) acrylate having an alkyl group with a carbon number of 8 or more, and the half value width X of the primary peak as measured by small angle X-ray scattering measurement of the (meth) acrylic copolymer (A) satisfies the following formula (i).

Description

Resin composition for adhesive and adhesive sheet

The present invention relates to a resin composition for an adhesive and an adhesive sheet.

This application claims priority based on Japanese Patent Application No. 2016-235193, which was filed in Japan on December 2, 2016, and the content is cited in this application.

Previously, by polymerizing vinyl monomers alone or copolymerizing two or more vinyl monomers, various copolymers with different physical properties were synthesized. Generally speaking, if it is a homopolymer of a vinyl monomer, it cannot meet the requirements of various physical properties. Therefore, copolymerization of two or more vinyl monomers or a mixture of two or more polymers is used. Methods. However, when only two or more vinyl monomers are copolymerized, there is a tendency to average the characteristics of each vinyl monomer unit. In addition, if only two or more kinds of polymers are mixed, these polymers are often not sufficiently mixed with each other, and the characteristics of each vinyl monomer unit are often impaired.

In response to this problem, studies on copolymers using macromonomers have been conducted. For example, in the field of adhesives, as a group using such copolymers As a result, the following are proposed.

(1) An adhesive composition comprising a macromonomer having a number average molecular weight ranging from 2,000 g/mole to 50,000 g/mole and an ethylenically unsaturated monomer which is dispersed in a specific solid component Copolymer in an aqueous medium (Patent Document 1).

(2) A resin composition for adhesives, which is obtained by copolymerizing an alkyl (meth)acrylate monomer with a macromonomer having a number average molecular weight of 1,000 to 200,000 and a glass transition temperature of 30°C to 150°C (Patent Document 2).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 2002/022755

[Patent Document 2] Japanese Patent Laid-Open No. 11-158450

However, with the copolymers described in Patent Document 1 to Patent Document 2, it is difficult to improve the retention and reduce the contamination of the substrate while maintaining the adhesive force in an appropriate range. For example, with regard to the adhesive layer attached to the substrate, the re-peelability under a high temperature environment or after a long period of time is not sufficient. When peeling from the substrate, a part of the adhesive layer remains on the attached surface. Caused by substrate contamination. In addition, if the cohesive force of the copolymer is increased, the viscosity when the adhesive is applied as a formulation becomes higher, and uneven coating is likely to occur. Therefore, it is necessary to increase the low molecular weight components such as the diluent solvent or diluting monomer, and the productivity is reduced. , Or the control of adhesive properties becomes difficult.

The present invention is made in view of the above circumstances, and its object is to provide a resin composition for an adhesive that can form an adhesive layer with sufficient holding power and an appropriate range of adhesive power and low substrate contamination due to glue residue And adhesive film.

The present invention has the following aspects.

[1] A resin composition for an adhesive, comprising: a (meth)acrylic copolymer having a structural unit derived from a macromonomer (a) and a structural unit derived from a vinyl monomer (b) ( A) Regarding the macromonomer (a), there are two or more structural units represented by the following formula (a') and are represented by the following formula (1),

The vinyl monomer (b) contains an alkyl (meth)acrylic acid alkyl ester (b1) with a carbon number of 8 or more, and the (meth)acrylic copolymer (A) has a small angle X The half-value width X of the primary peak measured by the ray scattering measurement satisfies the following formula (i).

0<X≦0.12‧‧‧(i)

(In the formula, R ¹ represents hydrogen atom, methyl or CH ₂ OH, R ² represents OR ³ , halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ , NHCOR ⁸ , or R ⁹ , R ³ ~R ⁸ each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted Or substituted heteroaryl, unsubstituted or substituted non-aromatic heterocyclic group, unsubstituted or substituted aralkyl, unsubstituted or substituted alkane Groups, unsubstituted or substituted organosilyl groups, or unsubstituted or substituted (poly)organosiloxyalkyl groups, the substituents in these groups are selected from alkyl groups and aryl groups, respectively , Heteroaryl, non-aromatic heterocyclic group, aralkyl group, alkaryl group, carboxylic acid group, carboxylate group, epoxy group, hydroxyl group, alkoxy group, primary amino group, secondary amino group, three At least one of the group consisting of a graded amine group, an isocyanate group, a sulfonic acid group and a halogen atom, R ⁹ represents an unsubstituted or substituted aryl group, or an unsubstituted or substituted group Heteroaryl groups, or unsubstituted or substituted non-aromatic heterocyclic groups, the substituents in these groups are selected from alkyl groups, aryl groups, heteroaryl groups, and non-aromatic heterocyclic groups, respectively , Aralkyl group, alkaryl group, carboxylic acid group, carboxylate group, epoxy group, hydroxyl group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, isocyanate group, sulfonic acid group , At least one of an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted alkene group, and a halogen atom. R Represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted group Heteroaryl groups, unsubstituted or substituted non-aromatic heterocyclic groups, unsubstituted or substituted aralkyl groups, unsubstituted or substituted alkaryl groups, unsubstituted or substituted alkaryl groups A substituted or substituted organosilyl group, or an unsubstituted or substituted (poly)organosiloxyalkyl group, Q represents a main chain part containing two or more structural units (a'), and Z represents End group)

[2] The resin composition for adhesives as described in [1], wherein the weight average molecular weight of the (meth)acrylic copolymer (A) is 1,000 to 1,000,000.

[3] The resin composition for adhesives as described in [1] or [2], wherein the content of the structural unit derived from the macromonomer (a) is 3% by mass relative to the total mass of all the structural units ~60% by mass.

[4] The resin composition for adhesives as described in any one of [1] to [3], wherein the number average molecular weight of the macromonomer (a) is 100 or more and 100,000 or less.

[5] The resin composition for adhesives as described in any one of [1] to [4], wherein the (meth)acrylic copolymer (A) satisfies the condition of formula (ii).

0.1≦X/Y≦0.50‧‧‧‧(ii)

(X represents the half-value width of the primary peak measured by small-angle X-ray scattering measurement, and Y represents the peak position of the one-dimensional scattering distribution)

[6] The resin composition for adhesives as described in any one of [1] to [5], wherein the Tga of the macromonomer (a) and the polymer obtained by polymerizing the vinyl monomer (b) The TgB satisfies the relationship of formula (4).

Tga-TgB>0℃‧‧‧(4)

[7] The resin composition for an adhesive as described in any one of [1] to [6], wherein the solubility parameter δa of the structural unit derived from the macromonomer (a) and the monomer derived from the vinyl monomer The solubility parameter δb of the structural unit of (b) satisfies the relationship of formula (5).

δa-δb>0‧‧‧(5)

[8] The resin composition for adhesives as described in any one of [1] to [7], wherein the (meth)acrylic copolymer (A) is made into a 50% ethyl acetate solution The viscosity of the solution is 10mPa. s~800,000mPa. s.

[9] An adhesive sheet using the resin composition for an adhesive as described in any one of [1] to [8].

According to the present invention, it is possible to provide a resin composition for an adhesive and an adhesive sheet that can form an adhesive layer with sufficient holding power and an appropriate range of adhesive power and low substrate contamination due to glue residue. In addition, according to the copolymer of the present invention, the viscosity of the formulation at the time of coating can be adjusted to an appropriate range.

The definitions of the following terms apply to this specification and the scope of the patent application.

The "vinyl monomer" refers to a monomer having an ethylenically unsaturated bond (polymerizable carbon-carbon double bond).

The "(meth)acrylic copolymer" refers to a copolymer in which at least a part of the structural unit is a structural unit derived from a (meth)acrylic monomer. The (meth)acrylic copolymer may further include a structural unit derived from a monomer (for example, styrene) other than the (meth)acrylic monomer.

The "(meth)acrylic monomer" refers to a monomer having a (meth)acrylic acid group.

"(Meth)acryloyl" is a general term for acrylic and methacryloyl.

"(Meth)acrylate" is a general term for acrylate and methacrylate. "(Meth)acrylic acid" is the general term for acrylic acid and methacrylic acid. "(Meth)acrylonitrile" is the general term for acrylonitrile and methacrylonitrile. "(Meth)acrylamide" is the general term for acrylamide and methacrylamide.

〔(Meth)acrylic copolymer〕

The (meth)acrylic copolymer (hereinafter also referred to as "copolymer (A)") contained in the resin composition for an adhesive of the present invention satisfies the following formula (i). That is, the half-value width X of the one-dimensional scattering peak in the small-angle X-ray scattering measurement exceeds 0 and is 0.12 or less. The half-value width X is preferably 0.01 to 0.12, more preferably 0.03 to 0.11, and still more preferably 0.05 to 0.10. If the half-value width X is less than the upper limit of the range, the adhesive layer using the copolymer (A) can have sufficient holding power, and the adhesive power will not be too high and maintain appropriate In the range, the substrate contamination caused by residual glue is low.

0<X≦0.12‧‧‧(i)

(In the formula, X represents the half-value width of the one-dimensional scattering peak in the small-angle X-ray scattering measurement of the copolymer (A))

The so-called small-angle X-ray scattering measurement refers to a method of obtaining nano-level (1nm~100nm) structural information by observing scattered X-rays with a scattering angle of a few degrees or less. In the present invention, as an indicator of the (micro)phase separation state of the copolymer, the half-value width X of the one-dimensional scattering peak in the small-angle X-ray scattering measurement is used. The details of the measuring method of the half-value width X are as shown in the later-mentioned Examples.

A value with a half-value width X means that a (micro)phase separation structure is formed in the sample (copolymer layer) for small-angle X-ray scattering measurement, that is, the copolymer (A) has a large amount of (micro)phase separation. Parts. Generally, such a plurality of parts respectively contain structural units with different properties.

In addition, the more clear or uniform the state of (micro)phase separation in the sample subjected to the small-angle X-ray scattering measurement, the sharper the shape of the one-dimensional scattering peak and the smaller the half-value width X tends to be. That is, the smaller the half-value width X, the lower the compatibility of the multiple parts of the copolymer (A), and the easier the (micro)phase separation is.

By distributing structural units with different properties in different parts to form a (micro)phase-separated structure, the characteristics of each structural unit are easily revealed. Therefore, it is possible to maintain an appropriate range of adhesion and increase cohesion to achieve an increase in retention and a reduction in substrate contamination.

The (micro)phase separation structure includes a lamellar structure, a gyroid structure, a cylinder structure, a sphere structure, etc., and may be any of these structures.

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

In addition, the (meth)acrylic copolymer (A) preferably satisfies the following formula (ii). That is, the ratio of the half-value width X of the one-dimensional scattering peak to the peak position Y of the one-dimensional scattering distribution in the small-angle X-ray scattering measurement is preferably 0.1 to 0.50. X/Y is more preferably 0.1 to 0.43, and still more preferably 0.2 to 0.40. If X/Y is equal to or more than the lower limit of the above-mentioned range, the coatability is more excellent, and the holding power is not too low. When X/Y is less than the upper limit of the said range, the adhesive force of an appropriate range can be maintained, and the retention and resistance to substrate contamination will be more excellent.

The peak position Y represents the distance between the domains of the microphase separation. When the distance between domains becomes narrow, X/Y tends to become smaller.

0.1<X/Y≦0.50‧‧‧(ii)

(In the formula, X is as described above, and Y represents the peak position of the one-dimensional scattering distribution in the small-angle X-ray scattering measurement of the copolymer (A))

The weight average molecular weight (Mw) of the (meth)acrylic copolymer (A) is 1,000 to 1,000,000, preferably 50,000 to 700,000, more preferably 70,000 to 500,000, further preferably 80,000 to 400,000, most preferably 100,000 to 330,000 . If the weight average molecular weight of the copolymer (A) is more than the lower limit of the range, it can be An adhesive layer with excellent retention and low substrate contamination is formed. If the weight average molecular weight of the copolymer (A) is equal to or less than the upper limit of the above-mentioned range, the adhesive resin composition or the coating composition containing the copolymer (A) has good coating properties.

The weight average molecular weight of the copolymer (A) is a standard polystyrene conversion value measured by gel filtration chromatography (Gel Permeation Chromatography, GPC). In detail, it can measure by the method described in the Example mentioned later.

When the copolymer (A) is made into a 50% by mass ethyl acetate solution, the viscosity measured by a B-type viscometer at 25°C (hereinafter also referred to as "solution viscosity") is preferably 10 mPa. s~800,000mPa. s, more preferably 100mPa. s~10,000mPa. s, more preferably 200mPa. s~7,000mPa. s, and more preferably 200mPa. s~5,000mPa. s, the best is 500mPa. s~3,500mPa. s. If the viscosity of the solution is more than the lower limit of the above-mentioned range, the holding power of the adhesive layer will be more excellent, and the substrate contamination will be lower. If the solution viscosity is equal to or lower than the upper limit of the above range, the coating properties, compatibility with other components and hot melt processability at the time of preparation are more excellent.

The copolymer (A) may have a crosslinked structure or may not have a crosslinked structure. In terms of the coatability of the copolymer (A) or the resin composition for adhesives containing it, the compatibility with other components when it is made into a formulation, or the hot-melt processability, it is preferred that it does not have Cross-linked structure.

The copolymer (A) contains a structural unit derived from a (meth)acrylic monomer.

Relative to the total mass (100% by mass) of all the structural units constituting the copolymer (A), the amount of the structural unit derived from the (meth)acrylic monomer in the copolymer (A) The content is preferably 20% by mass to 100% by mass, more preferably 40% by mass to 100% by mass.

One aspect of the copolymer (A) is a copolymer having a structural unit derived from a macromonomer (a) having a number average molecular weight of 100 or more and 100,000 or less, and a structural unit derived from a vinyl monomer (b) (Hereinafter also referred to as "copolymer (A1)").

Typically, the copolymer (A1) has a graft copolymer in which a polymer chain derived from a macromonomer (a) is bonded to a polymer chain containing a structural unit derived from a vinyl monomer (b) Or the structure of block copolymers.

Regarding the copolymer (A1), the composition of the monomer constituting the macromonomer (a) and the composition of the vinyl monomer (b) can adjust the polymer chain derived from the macromonomer (a), and The compatibility of the polymer chain containing the structural unit derived from the vinyl monomer (b) can further adjust the value of the half-value width X.

Generally, the composition of the monomer constituting the macromonomer (a) is different from the composition of the vinyl monomer (b). The composition indicates the type and content ratio of the monomer.

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

<Giant Cell (a)>

The macromonomer (a) is a compound having two or more structural units derived from a monomer having a radical polymerizable group (hereinafter also referred to as "monomer (a1)"), and is a compound having radical polymerization Additive reactive functional groups such as hydroxyl groups, isocyanate groups, epoxy groups, carboxyl groups, acid anhydride groups, amino groups, amide groups, thiol groups, and carbodiimide groups.

The single body (a1) will be described in detail later. The two or more structural units possessed by the macromonomer (a) may be the same or different.

In the case where the macromonomer (a) has the radical polymerizable group, the macromonomer (a) and the vinyl monomer (b) can be copolymerized by radical polymerization to obtain the copolymer (A1) ).

In the case where the macromonomer (a) has the addition-reactive functional group, usually the vinyl monomer (b) contains a vinyl monomer having a functional group capable of reacting with the addition-reactive functional group body. The functional group of the polymer containing the structural unit derived from this vinyl monomer (b) can be made to react with the macromonomer which has the said addition-reactive functional group, and the copolymer (A1) can be obtained.

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, a thiol group, or a carboxyl group.

Combination of epoxy group and amino group.

Combination of carboxyl group and epoxy group or carbodiimide group.

Combination of amine group and carboxyl group.

Combination of amide group and carboxyl group.

Combination of thiol group and epoxy group.

When the macromonomer (a) has a radical polymerizable group, the radical polymerizable group in the macromonomer (a) may be one or two or more, preferably one. In the case where the macromonomer (a) has the addition-reactive functional group, the addition-reactive functional group in the macromonomer (a) may contain one or more than two, preferably For one.

The macromonomer (a) may have any one of a radical polymerizable group and the functional group, or may have both. In the case of having both of the radical polymerizable group and the functional group, the radical polymerizable group and the functional group possessed by the macromonomer (a) may each be one or two or more.

The macromonomer (a) may have a radical polymerizable group and the functional group in the repeating unit, or may have a radical polymerizable group and the functional group at the end, so that the resin composition for the adhesive can be easily adjusted In terms of viscosity, etc., it is preferable to have it only at the end.

It is preferable that the macromonomer (a) has a radical polymerizable group in terms of copolymerization with the vinyl monomer (b). Compared with the case where the copolymer (A1) is a reaction product of a functional group of a polymer containing a structural unit derived from a vinyl monomer (b) and a macromonomer having the addition-reactive functional group, the copolymerization When the substance (A1) is a copolymer of a macromonomer (a) and a vinyl monomer (b), it is easy to control the amount of introduction of the macromonomer (a), or it can reduce the residual functional group caused by It is excellent in terms of corrosion.

The radical polymerizable group possessed by the macromonomer (a) is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include CH ₂ =C(COOR)-CH ₂ -, (meth)acryloyl group, 2-(hydroxymethyl)acryloyl group, vinyl group, and the like.

Here, R represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted Or substituted heteroaryl, unsubstituted or substituted non-aromatic heterocyclic group, unsubstituted or substituted aralkyl, unsubstituted or substituted alkane Group, unsubstituted or substituted organosilyl group, or unsubstituted or substituted (poly)organosiloxyalkyl group.

As the unsubstituted alkyl group in R, for example, a branched alkyl group or a linear alkyl group having 1 to 22 carbon atoms can be cited. Specific examples of branched or linear alkyl groups having 1 to 22 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, isobutyl, and pentyl. (amyl), isopentyl, hexyl, heptyl, 2-ethylhexyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl ( Lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl), isooctadecyl, nonadecyl, Eicosyl and behenyl, etc.

The unsubstituted alicyclic group in R may be monocyclic or polycyclic, for example, alicyclic group having 3 to 20 carbon atoms. The alicyclic group is preferably a saturated alicyclic group, and specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, cyclo Octyl, and adamantyl, etc.

Examples of the unsubstituted aryl group in R include aryl groups having 6 to 18 carbon atoms. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group and a naphthyl group.

As an unsubstituted heteroaryl group in R, a pyridyl group, a carbazolyl group, etc. are mentioned, for example.

As the unsubstituted non-aromatic heterocyclic group, for example, a pyrrolidinyl group, a pyrrolidinone group, an internal amino group, etc. can be mentioned.

Examples of unsubstituted aralkyl groups include benzyl and phenylethyl.

As the unsubstituted organosilyl group, for example, -SiR ¹⁷ R ¹⁸ R ¹⁹ (here, R ¹⁷ to R ¹⁹ each independently represent an unsubstituted or substituted alkyl group, an unsubstituted or substituted group) The alicyclic group, or unsubstituted or substituted aryl group).

Examples of the unsubstituted or substituted alkyl group in R ¹⁷ to R ¹⁹ include the same ones as described above, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. , N-octyl, n-dodecyl, stearyl, lauryl, isopropyl, isobutyl, sec-butyl, 2-methylisopropyl, benzyl, etc. As an unsubstituted or substituted alicyclic group, the same thing as mentioned above can be mentioned, for example, a cyclohexyl group etc. are mentioned. As the unsubstituted or substituted aryl group, the same as described above can be mentioned, for example, a phenyl group, a p-methylphenyl group, etc. can be mentioned. R ¹⁷ to R ¹⁹ may be the same or different.

As the unsubstituted (poly)organosiloxane group, for example, -SiR ³⁰ R ³¹ -OR ³² , -(SiR ³³ R ³⁴ -O-) _n -R ³⁵ (here, R ³⁰ to R ³⁵ are each It independently represents 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.}

As a substituent in R (a substituted alkyl group, a substituted alicyclic group, a substituted aryl group, a substituted heteroaryl group, a substituted non-aromatic heterocyclic group, The substituent in each of the substituted aralkyl group, the substituted alkaryl group, and the substituted organosilyl group), for example, can be selected from alkyl groups (where R is a substituted alkyl group Except), aryl group, -COOR ¹¹ , cyano ^{group, -OR 12} , -NR ¹³ R ¹⁴ , -CONR ¹⁵ R ¹⁶ , halogen atom, allyl group, epoxy group, siloxy group, and show hydrophilic or At least one of the group consisting of ionic groups.

Here, R ¹¹ to R ¹⁶ each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, or an unsubstituted or substituted group的aryl. For these groups, the same ones as described above can be cited, respectively.

Examples of the alkyl group and the aryl group in the substituent are the same as the unsubstituted alkyl group and the unsubstituted aryl group, respectively.

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

R ^{12 of -OR 12} in the substituent is preferably a hydrogen atom or an unsubstituted alkyl group. That is, -OR ^{12 is} preferably a hydroxyl group or an alkoxy group. As an alkoxy group, a C1-C12 alkoxy group is mentioned, for example, and a methoxy group is mentioned as a specific example.

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

^{As -CONR 15} R ¹⁶ in the substituent, for example _{, aminomethyl (-CONH 2} ), N-methylaminomethyl (-CONHCH ₃ ), and N,N-dimethylaminomethyl can be mentioned. Group (dimethylamino: -CON(CH ₃ ) ₂ ) and 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 that exhibits hydrophilicity or ionicity among the substituents include alkali salts of carboxyl groups or alkali salts of sulfonate groups, polyethylene oxide groups, polypropylene oxide groups, and other poly(epoxy groups). Cationic substituents such as alkyl) group and quaternary ammonium salt group.

As R, an unsubstituted or substituted alkyl group or an unsubstituted or substituted alicyclic group is preferred, and an unsubstituted alkyl group or an unsubstituted or substituted group is more preferred. An alicyclic group with an alkyl group as a substituent.

Among the above, in terms of ease of acquisition, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclo Propyl, cyclobutyl, isobornyl and adamantyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, iso Borneol and adamantyl.

As the radical polymerizable group possessed by the monomer (a1), similar to the preferred radical polymerizable group possessed by the macromonomer (a), a group having an ethylenically unsaturated bond is preferred. That is, the monomer (a1) is preferably a vinyl monomer.

As the monomer (a1), various monomers can be used, and for example, the following can be mentioned.

Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate Ester, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, ( Isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, Cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate , Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, terpene acrylate or its derivatives, hydrogenated rosin acrylate or its derivatives, dicyclopentenyl (meth)acrylate Dodecyl ester and other hydrocarbon group-containing (meth)acrylates; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate Hydroxy-containing (meth)acrylates such as 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, etc.; (meth)acrylic acid, hexahydrophthalic acid 2-(Meth)acryloyloxyethyl, hexahydrophthalic acid 2-(meth)acryloyloxypropyl ester, phthalic acid 2-(meth)acryloyloxyethyl, ortho 2-(meth)acryloxypropyl phthalate, 2-(meth)acryloxyethyl maleate, 2-(meth)acryloxypropyl maleate Ester, 2-(meth)acryloxyethyl succinate, 2-(meth)acryloxypropyl succinate, crotonic acid, fumaric acid, maleic acid, itaconic acid Acid, citraconic acid, cis-butine Monomethyl acrylate, monoethyl maleate, monooctyl maleate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monoethyl itaconate Carboxyl-containing ethylene such as octyl ester, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl citraconic acid, etc. Base monomer; maleic anhydride, itaconic anhydride and other acid anhydride group-containing vinyl monomers; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N, N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-tertiary butyl(meth)acrylamide, N-tertiary octyl(methyl) Acrylamide, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (Meth)acrylamide, diacetone (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (form Yl)acrylamide, N-vinylacetamide, maleic amide, N,N'-methylenebis(meth)acrylamide and other chain vinyl monomers containing amide linkages , (Meth)acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, maleimide and other cyclic vinyl monomers containing amide bonds Monomers containing amide bonds such as vinyl monomers; dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, coat Unsaturated dicarboxylic acid diester monomers such as dibutyl aconic acid and diperfluorocyclohexyl fumarate; (meth) glycidyl acrylate, α-ethyl glycidyl acrylate, (methyl) ) 3,4-epoxybutyl acrylate and other epoxy-containing vinyl monomers; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc. Amino (meth)acrylate vinyl monomers; Divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6- Hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene two Alcohol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10- Decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, allyl(meth)acrylate Polyfunctional vinyl monomers such as esters, triallyl cyanurate, diallyl maleate, and polypropylene glycol diallyl ether; heterocyclic monomers such as vinylpyridine and vinylcarbazole Weight body: polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, (meth)acrylic acid N-butoxyethyl, isobutoxyethyl (meth)acrylate, tertiary butoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, (meth) Phenoxyethyl acrylate, nonylphenoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, acetoxyethyl (meth)acrylate, "Prasel (Placcel)FM" (caprolactone addition monomer manufactured by Daicel Chemical Co., Ltd., trade name), "Blemmer PME-100" (Methoxy Base polyethylene glycol methacrylate (the ethylene glycol chain is 2), trade name), "Blemmer PME-200" (Methoxy polyethylene glycol manufactured by NOF Corporation) Methacrylate (ethylene glycol chain is 4), trade name), "Blemmer PME-400" (Methoxy polyethylene glycol methacrylate manufactured by NOF Corporation ( The chain of ethylene glycol is 9 ), trade name), "Blemmer 50POEP-800B" (octoxy polyethylene glycol-polypropylene glycol-methacrylate manufactured by NOF Corporation (the ethylene glycol chain is 8 and The chain of propylene glycol is 6), trade name), "Blemmer 20ANEP-600" (nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate manufactured by NOF Corporation, trade name) ), "Blemmer AME-100" (manufactured by NOF Corporation, trade name), "Blemmer AME-200" (manufactured by NOF Corporation, trade name) and "cloth Blemmer 50AOEP-800B" (manufactured by NOF Corporation, trade name) and other glycol ester monomers; 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth) Yl) acryloxy propyl methyl diethoxy silane, 3-(meth) acryloxy propyl triethoxy silane, 3-acryloxy propyl trimethoxy silane, vinyl trimethyl Monomers containing silane coupling agents such as oxysilane and vinyl triethoxy silane; trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tri-(meth)acrylate N-propyl silyl ester, tri-n-butyl silyl (meth) acrylate, tri-n-pentyl silyl (meth) acrylate, tri-n-hexyl silyl (meth) acrylate, tri-n-butyl silyl (meth) acrylate -N-octyl silyl ester, tri-n-dodecyl silyl (meth) acrylate, triphenyl silyl (meth) acrylate, tri-p-methylphenyl silyl (meth) acrylate, (meth) Base) tribenzyl silyl acrylate, triisopropyl silyl (meth) acrylate, triisobutyl silyl (meth) acrylate, tris-second butyl silyl (meth) acrylate, (meth) ) Tri-2-methyl isopropyl silyl acrylate, tri-tertiary butyl silyl (meth) acrylate, ethyl dimethyl silyl (meth) acrylate, n-butyl di (meth) acrylate Methyl silyl ester, diisopropyl-n-butyl silyl (meth)acrylate, n-octyl (meth)acrylate Di-n-butyl silane, diisopropyl stearyl silyl (meth)acrylate, dicyclohexylphenyl silyl (meth)acrylate, tert-butyl diphenyl silyl (meth)acrylate Esters, (meth) acrylate lauryl diphenyl silyl ester, maleic acid triisopropyl silyl methyl ester, maleic acid triisopropyl silyl pentyl ester, maleic acid tri- N-butyl silyl-n-butyl ester, maleic acid tert-butyl diphenyl silyl methyl ester, maleic acid tert-butyl diphenyl silyl-n-butyl ester, fumarate Triisopropylsilyl methyl ester, triisopropylsilylpentyl fumarate, tri-n-butylsilyl-n-butyl fumarate, tertiary butyl fumarate Diphenyl silyl methyl ester, tertiary butyl diphenyl silyl fumarate-n-butyl ester, Silaplane FM-0711 (manufactured by JNC (Stock), trade name), Celan Silaplane FM-0721 (manufactured by JNC (Stock), trade name), Silaplane FM-0725 (manufactured by JNC (Stock), trade name), Silaplane TM-0701 (Manufactured by JNC (Stock), trade name), Silaplane TM-0701T (manufactured by JNC (Stock), trade name), X-22-174ASX (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-174BX (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), KF-2012 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) ), X-22-2404 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) and other monomers containing silane coupling agents, monomers containing organosilyl groups; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene Halogenated olefins such as ethylene difluoride and chlorotrifluoroethylene; monomers containing isocyanate groups such as ethyl 2-isocyanate (meth)acrylate; 2,2,2-trifluoroethyl (meth)acrylate , (Meth) acrylic acid 2,2,3,3,3-pentafluorobenzene Ester, 2-(perfluorobutyl) ethyl (meth)acrylate, 3-(perfluorobutyl)-2-hydroxypropyl (meth)acrylate, 2-(perfluorohexyl) (meth)acrylate Ethyl, 3-perfluorohexyl-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2,2,3,3-Tetrafluoropropyl, (meth)acrylate 1H,1H,5H-octafluoropentyl ester, (meth)methacrylate 1H,1H,5H-octafluoropentyl ester, (methyl) )Acrylic 1H, 1H, 2H, 2H-Tridecafluorooctyl, (meth)acrylate 1H-1-(trifluoromethyl)trifluoroethyl, (meth)acrylate 1H,1H,3H-hexafluorobutane Fluorine-containing monomers such as esters, 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl (meth)acrylate (excluding halogenated olefins); 1-butan (meth)acrylate Oxyethyl, 1-(2-ethylhexyloxy)ethyl (meth)acrylate, 1-(cyclohexoxy)ethyl methacrylate, 2-tetrahydropyran (meth)acrylate Monomers with acetal structure; 4-methacryloxybenzophenone, styrene, α-methylstyrene, vinyl toluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate , Vinyl propionate and other vinyl monomers, etc.

Among these, as the monomer (a1) used in the macromonomer (a), methyl methacrylate, n-butyl methacrylate, Isobutyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate.

Monomers (a1) may be used singly, or two or more of them may be used in combination.

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

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

(In the formula, R ¹ represents hydrogen atom, methyl or CH ₂ OH, R ² represents OR ³ , halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ , NHCOR ⁸ or R ⁹ , R ³ ~R ⁸ Each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or Substituted heteroaryl group, unsubstituted or substituted non-aromatic heterocyclic group, unsubstituted or substituted aralkyl group, unsubstituted or substituted alkaryl group , Unsubstituted or substituted organosilyl groups, unsubstituted or substituted (poly)organosiloxyalkyl groups, the substituents in these groups are selected from alkyl, aryl, hetero Aryl groups, non-aromatic heterocyclic groups, aralkyl groups, alkaryl groups, carboxylic acid groups (COOH), carboxylic acid ester groups, epoxy groups, hydroxyl groups, alkoxy groups, primary amino groups, secondary amino groups, At least one of the group consisting of tertiary amine group, isocyanate group, sulfonic acid group (SO ₃ ^{H) and halogen atom, R 9} represents unsubstituted or substituted aryl group, unsubstituted Or a substituted heteroaryl group, or an unsubstituted or substituted non-aromatic heterocyclic group, the substituents in these groups are selected from alkyl, aryl, heteroaryl, and non-aromatic groups. Group heterocyclic group, aralkyl group, alkaryl group, carboxylic acid group, carboxylate group, epoxy group, hydroxyl group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, isocyanic acid Group, sulfonic acid group, unsubstituted or substituted alkyl group, unsubstituted or substituted aryl group, unsubstituted or substituted alkene group and halogen atom At least one of)

R ³ ~ R ⁸ in the unsubstituted alkyl group, unsubstituted alicyclic group, unsubstituted aryl group, unsubstituted heteroaryl group, unsubstituted non-aromatic heterocyclic group, The unsubstituted aralkyl group, unsubstituted alkaryl group, unsubstituted organosilyl group, and unsubstituted (poly)organosiloxyalkyl group are respectively the same as those listed in R above.

Substituents in R ³ to R ⁸ (alkyl groups with substituents, alicyclic groups with substituents, aryl groups with substituents, heteroaryl groups with substituents, non-aromatic heterocycles with substituents Formula group, substituted aralkyl group, substituted alkaryl group, substituted organosilyl group in each of the substituent) in the alkyl group, aryl group, heteroaryl group, non-aromatic heterocyclic ring The formula group, aralkyl group, alkaryl group, and halogen atom may be the same as those described above.

As the carboxylate group, for example, R ^{11 of the -COOR 11} is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, or an unsubstituted or A group of an aryl group having a substituent.

As the alkoxy group, R ¹² -OR ¹² include the unsubstituted alkyl group.

As the secondary amino group, R ^{13 of the -NR 13} R ¹⁴ is a hydrogen atom, R ¹⁴ is an unsubstituted or substituted alkyl group, and an unsubstituted or substituted alicyclic group. , Or unsubstituted or substituted aryl group.

As the tertiary amino group, R ¹³ and R ^{14 of the -NR 13} R ¹⁴ are each an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, or Unsubstituted or substituted aryl group.

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

The carboxylate group and the alkoxy group in the substituents in R ⁹ (substituents in each of the substituted aryl group, the substituted heteroaryl group, and the substituted non-aromatic heterocyclic group) , Primary amine group, secondary amine group, tertiary amine group, unsubstituted or substituted alkyl group, unsubstituted or substituted aryl group, and halogen atom may be the same as described above .

As an unsubstituted alkene group, an allyl group etc. are mentioned, for example.

As the substituent in the alkene group having a substituent, the same as the substituent in ^{R 9 can be mentioned.}

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

As _{specific examples of CH 2} =CR ¹ R ² , the following can be cited.

Substituted or unsubstituted alkyl (meth)acrylate [for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate , N-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, ( Stearyl (meth)acrylate, isostearyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, behenyl (meth)acrylate, (meth) ) 1-methyl-2-methoxyethyl acrylate, 3-methoxybutyl (meth)acrylate, (meth)acrylic acid 3-Methyl-3-methoxybutyl ester], substituted or unsubstituted aralkyl (meth)acrylate [e.g., benzyl (meth)acrylate, m-methoxybenzene (meth)acrylate Ethyl ethyl, p-methoxyphenyl ethyl (meth)acrylate], substituted or unsubstituted aryl (meth)acrylate [e.g., phenyl (meth)acrylate, m-(meth)acrylate Methoxyphenyl ester, p-methoxyphenyl (meth)acrylate, o-methoxyphenylethyl (meth)acrylate], alicyclic (meth)acrylate [for example, (meth)acrylic acid Isobornyl ester, cyclohexyl (meth)acrylate], (meth)acrylate containing halogen atoms [e.g. trifluoroethyl (meth)acrylate, perfluorooctyl (meth)acrylate, (meth) )Perfluorocyclohexyl acrylate] and other hydrophobic group-containing (meth)acrylate monomers; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, ( Meth) 2-butoxy ethyl acrylate, butoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol (methyl) ) Acrylate, phenoxyethyl (meth)acrylate, 2-(2-ethylhexyloxy)ethyl (meth)acrylate and other oxyethylene-containing (meth)acrylate monomers; ( Hydroxy-containing (meth)acrylate monomers such as 2-hydroxyethyl meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, etc. Weight body; methoxy polyethylene glycol allyl ether, methoxy polypropylene glycol allyl ether, butoxy polyethylene glycol allyl ether, butoxy polypropylene glycol allyl ether, methoxy polyethylene glycol -Polypropylene glycol allyl ether, butoxy polyethylene glycol-polypropylene glycol allyl ether and other terminal alkoxy allylated polyether monomers; glycidyl (meth)acrylate, α-ethyl acrylate glycidyl Glycerides, (methyl) Epoxy-containing vinyl monomers such as 3,4-epoxybutyl acrylate; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-di Ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-tertiary butyl (meth)acrylamide, N-octyl (meth)acrylamide , N-hydroxymethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (methyl) )Acrylamide, diacetone (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)propylene Amide, N-vinylacetamide, N,N'-methylenebis(meth)acrylamide, (meth)acrylomorpholine, N-vinylpyrrolidone, N-vinyl -ε-Caprolactam and other vinyl monomers containing amide bonds; (meth)butylamino ethyl acrylate and other vinyl monomers containing primary or secondary amino groups; (methyl )Dimethylaminoethyl acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, ( (Meth)acrylic acid dibutylaminoethyl and other vinyl monomers containing tertiary amino groups; heterocyclic basic monomers such as vinylpyridine and vinylcarbazole; (meth)acrylic acid trimethyl Silane ester, triethyl silyl (meth) acrylate, tri-n-propyl silyl (meth) acrylate, tri-n-butyl silyl (meth) acrylate, tri-n-pentyl (meth) acrylate Silane ester, tri-n-hexyl silyl (meth)acrylate, tri-n-octyl silyl (meth)acrylate, tri-n-dodecyl silyl (meth)acrylate, triphenyl (meth)acrylate Silyl ester, tri-p-methylphenyl silyl (meth)acrylate, tribenzyl silyl (meth)acrylate, triisopropyl silyl (meth)acrylate, (meth) Triisobutyl silyl acrylate, tri-t-t-butyl silyl (meth) acrylate, tri-2-methyl isopropyl silyl (meth) acrylate, tri-tert-butyl (meth) acrylate Silane ester, ethyl dimethyl silyl (meth) acrylate, n-butyl dimethyl silyl (meth) acrylate, diisopropyl-n-butyl silyl (meth) acrylate, (meth) N-octyl di-n-butyl silyl acrylate, diisopropyl stearyl silyl (meth) acrylate, dicyclohexyl phenyl silyl (meth) acrylate, tertiary butyl di (meth) acrylate Phenyl silyl ester, lauryl diphenyl silyl (meth)acrylate and other vinyl monomers containing organosilyl groups; methacrylic acid, acrylic acid, vinyl benzoic acid, (meth)acrylic acid tetrahydrophthalic acid Monohydroxyethyl formate, monohydroxypropyl tetrahydrophthalate (meth)acrylate, monohydroxybutyl tetrahydrophthalate (meth)acrylate, monohydroxyethyl (meth)acrylate phthalate Ester, (meth)acrylate monohydroxypropyl phthalate, (meth)acrylate monohydroxyethyl succinate, (meth)acrylate succinate monohydroxypropyl, (meth)acrylate maleic acid Carboxyl group-containing ethylenically unsaturated monomers such as monohydroxyethyl and (meth)acrylate maleic acid monohydroxypropyl; cyano group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; alkanes Vinyl ether [for example, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, 2-ethylhexyl vinyl ether, etc.], cycloalkyl vinyl ether [for example, Cyclohexyl vinyl ether, etc.] and other vinyl ether monomers; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and other vinyl ester monomers; styrene, vinyl toluene, α-methyl Aromatic vinyl monomers such as styrene; Halogenated olefins such as vinyl chloride and vinyl fluoride, etc.

The macromonomer (a) may have other structural units other than the structural unit (a'). As another structural unit, for example, a structural unit derived from a single body that does not correspond to CH ₂ =CR ¹ R ² in the single body listed as an example of the above-mentioned single body (a1) can be cited.

Preferred specific examples of other structural units include structural units derived from the following monomers.

Triisopropylsilyl methyl maleate, triisopropylsilylpentyl maleate, tri-n-butylsilyl-n-butyl maleate, maleic acid Tertiary butyl diphenyl silyl methyl ester, tertiary butyl diphenyl silyl maleate-n-butyl ester, triisopropyl silyl methyl fumarate, fumaric acid Triisopropylsilyl amyl ester, fumarate tri-n-butylsilyl-n-butyl ester, fumarate tert-butyldiphenylsilyl methyl ester, fumarate tertiary Butyldiphenylsilyl-n-butyl ester and other vinyl monomers containing organosilyl groups; maleic anhydride, itaconic anhydride and other vinyl monomers containing acid anhydride groups; crotonic acid, fumarene Diacid, Itaconic acid, Maleic acid, Citraconic acid, Monomethyl maleate, Monoethyl maleate, Monobutyl maleate, Monomaleic acid Octyl ester, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, trans Ethylene unsaturated monomers containing carboxyl groups such as monobutyl butenedioate, monooctyl fumarate, and monoethyl citraconic acid; dimethyl maleate, dimaleate Butyl ester, dimethyl fumarate, Monomers of unsaturated dicarboxylic acid diesters such as dibutyl fumarate, dibutyl itaconate, and diperfluorocyclohexyl fumarate; vinylidene chloride, vinylidene fluoride, chlorine Halogenated olefins such as trifluoroethylene; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth) )Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9- Nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Multifunctional monomers such as hexa(meth)acrylate, allyl methacrylate, triallyl cyanurate, diallyl maleate, and polypropylene glycol diallyl ether.

With respect to the total mass (100% by mass) of all the structural units constituting the macromonomer (a), the macromonomer (a) preferably contains a structure derived from a (meth)acrylic monomer at 50% by mass or more The unit more preferably contains 70% by mass or more. The upper limit is not particularly limited, and may be 100% by mass.

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

The macromonomer (a) is preferably a macromonomer having a radical polymerizable group introduced at the end of the main chain containing two or more structural units (a'), and more preferably the following formula (1 ) Represents the giant monomer. By using the macromonomer of this structure, an adhesive layer with excellent holding power and low substrate contamination can be formed.

[化4]

(In the formula, R represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted Or substituted heteroaryl, unsubstituted or substituted non-aromatic heterocyclic group, unsubstituted or substituted aralkyl, unsubstituted or substituted alkane Aryl, unsubstituted or substituted organosilyl group, or unsubstituted or substituted (poly)organosiloxyalkyl group, Q represents a main body containing two or more structural units (a') Chain part, Z represents the end group)

In formula (1), R is the same as R in CH ₂ =C(COOR)-CH ₂ -described above, and preferred aspects are also the same.

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

Q may include only the structural unit (a'), or may further include other structural units than the structural unit (a').

^{Q preferably includes a structural unit in which R 1} is a hydrogen atom or a methyl group and R ² is COOR ⁵ in the formula (a') as the structural unit (a'). The ratio of the structural unit relative to the total mass (100% by mass) of all the structural units constituting Q is preferably 50% by mass or more, more preferably 70% by mass or more, and may be 100% by mass.

The number of structural units constituting Q can be appropriately set so that the number average molecular weight of the macromonomer (a) falls within the aforementioned range.

As Z, for example, similar to the terminal group of the polymer obtained by known radical polymerization, a hydrogen atom, a radical polymerization initiator-derived group, a radical polymerizable group, and the like can be mentioned.

The macromonomer (a) is particularly preferably a macromonomer represented by the following formula (2).

(In the formula, R and Z respectively have the same meaning as described above, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted group Alicyclic groups, unsubstituted or substituted aryl groups, unsubstituted or substituted heteroaryl groups, unsubstituted or substituted non-aromatic heterocyclic groups, unsubstituted or substituted heteroaryl groups, Substituted or substituted aralkyl group, unsubstituted or substituted alkaryl group, unsubstituted or substituted organosilyl group, or unsubstituted or substituted (poly) Organosiloxane alkyl groups, the substituents in these groups are selected from alkyl groups, aryl groups, heteroaryl groups, non-aromatic heterocyclic groups, aralkyl groups, alkaryl groups, carboxylic acid groups, and carboxylic acid esters. At least one of the group consisting of an epoxy group, an epoxy group, a hydroxyl group, an alkoxy group, a primary amino group, a secondary amino group, a tertiary amino group, an isocyanate group, a sulfonic acid group, and a halogen atom, n represents 2 The above natural numbers, Z represents the end group)

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

The groups in R ²² are the same as those listed in R ^{5 of COOR 5.}

n is a natural number of 2 or more. n is preferably in the range of 100 or more and 100,000 or less of the number average molecular weight (Mn) of the macromonomer (a). The preferable range of the number average molecular weight is as follows. The n pieces of R ²¹ may be the same or different. The n pieces of R ²² 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 structural unit derived from the vinyl monomer (b), The macromonomer (a) preferably has one or more of the addition-reactive functional groups and two or more of the structural units (a'). As the structural unit (a'), the same as the case where the macromonomer (a) has a radical polymerizable group can be used.

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

The number average molecular weight (Mn) of the macromonomer (a) is preferably 100 or more And below 100,000, more preferably 800 to 30,000, further preferably 900 to 10,000, particularly preferably 1,000 to 6,000, most preferably 1,000 to 5,000. If the number average molecular weight of the macromonomer (a) is more than the lower limit of the above-mentioned range, the holding power of the adhesive layer is more excellent. If the number average molecular weight of the macromonomer (a) is less than the upper limit of the above-mentioned range, the adhesive force of the adhesive layer becomes an appropriate value, and the compatibility with other components and heat when the adhesive formulation is made The melt workability is more excellent.

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

The glass transition temperature (hereinafter also referred to as "Tga") of the giant monomer (a) is preferably 0°C to 150°C, more preferably 10°C to 120°C, and still more preferably 30°C to 100°C. If Tga is more than the lower limit of the said range, the holding force of an adhesive layer will be more excellent. If Tga is equal to or less than the upper limit of the above-mentioned range, the hot melt processability is more excellent.

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

The Tga can be adjusted by the composition of the monobody forming the macromonomer (a).

Regarding the macromonomer (a), one manufactured by a known method can be used, or a commercially available one can also be used.

As a method of producing the macromonomer (a) having a radically polymerizable group, for example, a method of producing using a cobalt chain transfer agent, and using an α-substituted unsaturated compound such as α-methylstyrene dimer as the chain transfer The method of reagent, the method of using the initiator, the method of chemically bonding the radical polymerizable group to the polymer, the method of using thermal decomposition, etc.

Among these, as a method for producing the macromonomer (a) having a radical polymerizable group, In terms of a small number of production steps and a high chain transfer constant of the catalyst used, a method of production using a cobalt chain transfer agent is preferred. In addition, the macromonomer (a) in the case of manufacturing using a cobalt chain transfer agent has a structure represented by the above-mentioned formula (1).

As a method of producing the macromonomer (a) using a cobalt chain transfer agent, for example, an aqueous dispersion polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be cited. In terms of the simplicity of the recovery step, the aqueous dispersion polymerization method is preferred.

As a method of chemically bonding a radically polymerizable group to a polymer, for example, a method of manufacturing by substituting a compound having a radically polymerizable carbon-carbon double bond for the halogen group of a polymer having a halogen group, A method of reacting a vinyl monomer having an acid group with a vinyl polymer having an epoxy group, a method of reacting a vinyl monomer having an epoxy group with a vinyl monomer having an acid group, A method of reacting a vinyl polymer of a hydroxyl group with a diisocyanate compound to obtain a vinyl polymer having an isocyanate group and reacting the vinyl polymer with a vinyl monomer having a hydroxyl group can be produced by any method.

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

Method for producing macromonomers (a) having addition-reactive functional groups such as hydroxyl groups, isocyanate groups, epoxy groups, carboxyl groups, acid anhydride groups, amino groups, amide groups, thiol groups, and carbodiimide groups Examples include: a method of copolymerizing a vinyl monomer having the functional group; or a method of using a chain transfer agent such as mercaptoethanol, thioglycolic acid, and mercaptopropionic acid; using a method that can introduce 2,2'-azobis( Propane-2-carboxamidine), 4,4'-azobis(4- Cyanovaleric acid), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine], 2,2'-azobis[2-[1-(2- Hydroxyethyl)-2-imidazolin-2-yl]propane] and other functional group initiators.

<Vinyl Monomer (b)>

The vinyl monomer (b) is a monomer having an ethylenically unsaturated bond and is not a macromonomer. The vinyl monomer (b) is not particularly limited, and the same monomers (a1) listed above for obtaining the macromonomer (a) can be used. The vinyl monomer (b) may be used singly, or two or more of them may be used in combination.

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

In the case where the macromonomer (a) is added to a polymer containing structural units derived from the vinyl monomer (b), the vinyl monomer (b) suitably contains a macromonomer (a) compatible with the macromonomer (a). ) Is a functional group that reacts with the functional group.

The vinyl monomer (b) is preferably an alkyl (meth)acrylate containing an unsubstituted alkyl group having 8 to 30 carbon atoms (hereinafter also referred to as "monomer (b1)"). With the single body (b1), the flexibility as an adhesive can be expressed, or the adhesive force can be maintained in an appropriate range to suppress residual glue. In addition, the single body (b1) is hydrophobic, so the single body (b1) can also suppress the water absorption or lower the relative permittivity. Furthermore, when the copolymer (A1) is used in a resin composition for an adhesive containing a polymerizable monofunctional compound, such as the resin composition for an adhesive (1) described later, a vinyl monomer (b) Containing the monomer (b1), the copolymer (A1) has more excellent compatibility with the polymerizable monofunctional compound. That is, as a polymerizable monofunctional compound, the details Although it will be mentioned later, the polymerizable monofunctional compound which has a C8 or more hydrocarbon group is used in many cases. The monomer (b1) has an alkyl group with 8 to 30 carbons, so the copolymer (A1) contains structural units derived from the monomer (b1) to improve compatibility with such polymerizable monofunctional compounds . If the copolymer (A1) has high compatibility with the polymerizable monofunctional compound, the transparency of the adhesive layer formed of the adhesive resin composition is further improved, and it is called Optical Clear Adhesive (OCA). ) Is useful for applications requiring optical transparency, such as a transparent double-sided adhesive sheet called liquid OCA (LOCA), and a liquid transparent adhesive called liquid OCA (LOCA).

Specific examples of the monomer (b1) include 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, and nonyl (meth)acrylate , Isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, (meth)acrylic acid Stearyl ester, isostearyl (meth)acrylate, behenyl (meth)acrylate, etc.

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

The vinyl monomer (b) may further contain other vinyl monomers other than the monomer (b1) as necessary. As other vinyl monomers, it can be appropriately selected from the monomers listed above.

For example, from the viewpoint of improving the cohesive force of the adhesive, one or more monomers selected from the group consisting of methyl (meth)acrylate and ethyl (meth)acrylate may be included.

From the viewpoint of improving adhesion, resistance to damp and heat whitening and low corrosion, it can also be Contains a vinyl monomer containing an amide bond. The so-called damp and heat resistance to whitening refers to the property that the adhesive layer or the like is not easily whitened when exposed to a high temperature and high humidity environment. As the vinyl monomer containing an amide bond, the same ones as described above can be mentioned.

In addition, preferred other vinyl monomers include (meth)acrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, styrene, and isobornyl (meth)acrylate. , Cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc.

As described above, the composition of the vinyl monomer (b) is generally different from the composition of the monomer constituting the macromonomer (a).

The vinyl monomer (b) is preferably a polymer obtained by polymerizing only the vinyl monomer (b) (hereinafter also referred to as "polymer (B)") and the macromonomer (a) A composition that produces a difference in polarity between. If there is a difference in polarity between the polymer (B) and the macromonomer (a), the half-value width X is likely to fall within the above-mentioned range. If the half-value width X is within the above range, the polymer chains of the macromonomer (a) and the polymer chains formed by the polymer (B) will be microphase separated when forming the adhesive layer or coating film, which is easy to Fully show their respective characteristics. For example, the effect of improving the retention of the adhesive layer by the giant monomer (a) is fully utilized, and the retention of the adhesive layer is excellent.

As an example of a composition that causes a difference in polarity, a macromonomer (a) includes a structural unit derived from methyl methacrylate, and a vinyl monomer (b) includes a monomer (b1). Since the monobody (b1) has a large number of carbon atoms in the alkyl group, it has a lower polarity than methyl methacrylate. With such a composition, a difference in polarity between the polymer (B) and the macromonomer (a) is generated.

In this example, the ratio of the structural unit derived from methyl methacrylate to the total of all structural units constituting the macromonomer (a) is preferably 50% by mass or more, more preferably 75% by mass or more. In addition, the ratio of the monomer (b1) to the total amount of the vinyl monomer (b) is preferably 30% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, and particularly preferably More than 90% by mass. The greater the ratio of the structural unit derived from methyl methacrylate in the macromonomer (a), or the greater the ratio of the monomer (b1) in the vinyl monomer (b), the higher the ratio of the polymer (B The greater the difference in polarity between) and the macromonomer (a), the easier it is for microphase separation to occur, so that the adhesive layer has excellent holding power and is less likely to produce residual glue.

In addition, in this example, from the viewpoint of increasing the difference in polarity, the vinyl monomer (b) has a carboxyl group, a hydroxyl group, an amide group, and an amine relative to the total amount of the vinyl monomer (b). The content of the vinyl monomer of a polar functional group such as a group is preferably 30% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less. The lower limit is not particularly limited, and may be 0% by mass.

The vinyl monomer (b) preferably has a composition in which the glass transition temperature (TgB) of the polymer (B) obtained by polymerizing only the vinyl monomer (b) is -100°C to 10°C. TgB is preferably -65°C to 0°C, more preferably -60°C to -10°C. If TgB is in the above range, the resin composition for an adhesive containing the copolymer (A1) has moderate flexibility and viscosity.

In the case of one type of vinyl monomer (b), TgB refers to the glass transition temperature of the homopolymer of the vinyl monomer, and in the case of multiple types of vinyl monomer (b), TgB is Refers to the glass based on the homopolymers of various vinyl monomers The glass transition temperature and mass fraction are calculated by Fox's calculation formula.

In addition, the calculation formula of Fox is the calculated value obtained by the following formula. You can use the "Polymer HandBook" [Polymer HandBook, J. Brandrup, Interscience] , 1989]. (Tg in the formula corresponds to TgB).

1/(273+Tg)=Σ(Wi/(273+Tgi)) (where Wi represents the mass fraction of monomer i, and Tgi represents the glass transition temperature (℃) of the homopolymer of monomer i)

In terms of fully expressing the respective characteristics of the macromonomer (a) part and the part including the structural unit derived from the vinyl monomer (b), the above-mentioned Tga and TgB preferably have the following Describe the relationship of formula (3). That is, it is preferable that Tga-TgB>0°C.

Tga>TgB‧‧‧(3)

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

<Content of each structural unit>

With respect to the total mass of all the structural units constituting the copolymer (A1), the content of the structural unit derived from the macromonomer (a) in the copolymer (A1) is preferably 3% by mass to 60% by mass, more preferably 7 mass% to 40 mass%, more preferably 8 mass% to 30 mass%, particularly preferably 9 mass% to 20 mass%. If it is derived from the structure of a macromonomer (a) The content of the unit is more than the lower limit of the above-mentioned range, and the holding power of the adhesive layer is more excellent. If the content of the structural unit derived from the macromonomer (a) is equal to or less than the upper limit of the above-mentioned range, the coating properties, compatibility with other components, and hot melt processability when used as a formulation are more excellent.

Relative to the total mass of all the structural units constituting the copolymer (A1), the content of the structural unit derived from the vinyl monomer (b) in the copolymer (A1) is preferably 40% by mass to 97% by mass, and more It is preferably 60% by mass to 93% by mass, more preferably 70% by mass to 92% by mass, and particularly preferably 80% by mass to 91% by mass. If the content of the structural unit derived from the vinyl monomer (b) is more than the lower limit of the above-mentioned range, the coating properties, compatibility with other components or hot melt processability when made into formulations are improved. Excellent. If the content of the structural unit derived from the vinyl monomer (b) is equal to or less than the upper limit of the above-mentioned range, the holding power of the adhesive layer is more excellent.

<Method for manufacturing copolymer (A1)>

As a manufacturing method of the copolymer (A1), the following manufacturing method (α), manufacturing method (β), etc. are mentioned, for example. The copolymer (A1) may be produced by the production method (α), or may be produced by the production method (β). However, the manufacturing method of the copolymer (A1) is not limited to these.

Production method (α): A method in which a macromonomer having a radical polymerizable group is used as the macromonomer (a), and the macromonomer (a) and the vinyl monomer (b) are copolymerized.

Production method (β): Use the macromonomer having the addition-reactive functional group as the macromonomer (a), and make the macromonomer (a) and the structure containing the vinyl monomer (b) The method for reacting the polymer of the unit, the vinyl monomer (b) contains A vinyl monomer having a functional group capable of reacting with the addition-reactive functional group.

In these production methods, 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), and the copolymer (A1) The weight average molecular weight, etc., can adjust the compatibility of the polymer chain derived from the macromonomer (a) and the polymer chain containing the structural unit derived from the vinyl monomer (b) to obtain the half-value width X The copolymer (A1) that satisfies the above formula (i).

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) will affect the compatibility. The larger the difference in polarity, the lower the compatibility and the smaller the half-value width X tends to be. In addition, the larger the number average molecular weight of the macromonomer (a) or the larger the weight average molecular weight of the copolymer (A1), the smaller the half-value width X tends to be.

From the viewpoint of setting the half-value width X of the copolymer (A) to be more than 0 and 0.12 or less, the solubility parameter δa derived from the structural unit of the macromonomer (a) and the monomer derived from the vinyl monomer ( The solubility parameter δb of the structural unit of b) preferably satisfies (δa-δb)>0. That is, it is preferable that the difference between δa and δb exceeds zero. It is more preferable to satisfy (δa-δb)≧0.30, and it is still more preferable to satisfy (δa-δb)≧0.60.

The solubility parameter δ can be obtained by the following formula (I).

δ=Σ(mi δi)‧‧‧(I)

In formula (I), mi represents the molar fraction of monomer i constituting the structural unit derived from the macromonomer (a) or the structural unit derived from the vinyl monomer (b), and δi represents the single The solubility parameter of volume i.

Monomer i is the monomer constituting the structural unit derived from the macromonomer (a) when δ is δa, and the monomer i is the monomer constituting the structural unit derived from the vinyl monomer (b) The δ at time is δb.

In addition, the solubility parameter (δi) of the monomer i can be calculated by the following formula (II).

δi={Σ(nj Ej)/Σ(nj Vj)}1/2‧‧‧(II)

In the formula (II), nj represents the number of atomic groups j constituting the singular body i, Ej represents the aggregation energy (J/mol) of the atomic group j, and Vj represents the molar volume of the atomic group j (cm ³ /mol). Furthermore, Ej and Vj are values quoted from "Polym. Eng. Sci." (1974) by RF Fedors. The solubility parameter δa of the structural unit derived from the macromonomer (a) and the solubility parameter δb of the structural unit derived from the vinyl monomer (b) in the copolymer (A) satisfy the above, and the half value When the width X exceeds 0 and is 0.12 or less, the adhesive layer using the copolymer (A) maintains an appropriate adhesive force and has a good retention force.

In addition, the X/Y ratio can be adjusted by the number or number average molecular weight of polymer chains derived from the macromonomer (a). Specifically, if the amount of polymer chains derived from the macromonomer (a) is increased or the number average molecular weight of the polymer chains derived from the macromonomer (a) is decreased, X/Y tends to decrease. .

As a manufacturing method of the copolymer (A1), the manufacturing method (α) is preferable. That is, the copolymer (A1) is preferably a copolymer of the macromonomer (a) and the vinyl monomer (b). In this copolymer, the structural unit derived from the macromonomer (a) and the structural unit derived from the vinyl monomer (b) are arranged randomly. That is, one or more polymer chains derived from the macromonomer (a) are bonded to the entire main chain of the copolymer (A1). This type of polymer has adhesion, for example, only when the end of the polymer chain containing the structural unit derived from the vinyl monomer (b) is bonded with the structural unit derived from the macromonomer (a). The layer retention tends to become better.

(Manufacturing method (α))

The composition of the monomers to be polymerized in the manufacturing method (α), that is, the types of monomers to be polymerized and the content (mass%) (addition) of each monomer relative to the total mass of all monomers. The preferred range is the same as the composition of the copolymer (A1), that is, the type of structural unit derived from the monomer constituting the copolymer (A1) and the content (mass %) of each structural unit relative to the total mass of all structural units.

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

The polymerization of the monomer can be carried out by a known method using a known polymerization initiator. For example, a method of reacting the macromonomer (a) and the vinyl monomer (b) in the presence of a radical polymerization initiator at a reaction temperature of 60° C. to 120° C. for 1 hour to 14 hours can be cited. A chain transfer agent can be used as needed during polymerization.

As the polymerization method, for example, a solution polymerization method, a suspension polymerization method, Known polymerization methods such as bulk polymerization method and emulsion polymerization method. It is preferable that the resin composition for adhesives containing the copolymer (A) does not contain water in terms of drying properties and coating film performance in the film forming step. The amount of water in the resin composition for an adhesive is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 1% by mass or less. The amount of water in the resin composition for adhesives can be measured by the volumetric Kcal Fisher method. Furthermore, in order to reduce the water content in the resin composition for adhesives, it is preferable that it does not contain water in the manufacturing process of a copolymer (A). The water content in the production step 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 may be 0% by mass. As a production method that does not contain water in the production step of the copolymer (A), a solution polymerization method is preferred.

Solution polymerization can be carried out by supplying a polymerization solvent, monomer, and radical polymerization initiator to the polymerization vessel, and maintaining it at a predetermined reaction temperature. Monomers can be added to the polymerization vessel in advance (before the inside of the polymerization vessel is set to the predetermined reaction temperature), or may be added dropwise after the inside of the polymerization vessel is set to the predetermined reaction temperature, or a part of it may be preliminarily added to the polymerization vessel. It is added to the polymerization vessel, and the remaining part is supplied dropwise.

For the copolymer (A), the weight average molecular weight is 1,000 to 1,000,000 and satisfies the formula (i), so it can form a substrate with sufficient holding power and an appropriate range of adhesion, and contamination of the substrate caused by residual glue Low-performance adhesive layer. Since it has sufficient holding power and an appropriate range of adhesive force, it is not easy to cause defects such as positional deviation after the components are attached to each other through the adhesive layer. When a protective sheet provided with the adhesive layer is prepared, the protective sheet is easily torn off, and it is not easy to produce substrate contamination after tearing off.

In terms of exerting the above-mentioned effects, the copolymer (A) is useful in the use of a resin composition for adhesives. Especially suitable for use as an adhesive sheet.

However, the use of the copolymer (A) is not limited to the above, and it can also be used for other uses. As other applications, for example, a coating composition, a resin composition for an adhesive, a composition for a molding material, a composition for a film, and the like can be cited.

〔Resin composition for adhesives〕

The resin composition for adhesives of this invention contains the said copolymer (A).

The copolymer (A) contained in the resin composition for adhesives may be one type or two or more types. The resin composition for adhesives of the present invention may contain only the (meth)acrylic copolymer (A), or may contain other components as needed.

<Polymerizable monofunctional compound>

The resin composition for an adhesive of the present invention may further include a polymerizable monofunctional compound having one radical polymerizable group as necessary.

Examples of the radical polymerizable group in the polymerizable monofunctional compound include the same ones as described above, and a (meth)acryloyl group is preferred. That is, the polymerizable monofunctional compound is preferably a monofunctional (meth)acrylate having one (meth)acryloyl group.

As the polymerizable monofunctional compound, the same monomers as those listed above for obtaining the macromonomer (a) can be used.

As the polymerizable monofunctional compound, in terms of flexibility as an adhesive, etc., a polymerizable monofunctional compound having a hydrocarbon group with 4 or more carbon atoms is preferred. As this hydrocarbon group, an alkyl group, an aryl group, an aralkyl group, etc. are mentioned. The carbon number of the hydrocarbon group is more preferably 8-30.

When the resin composition for adhesives of the present invention is used as a resin composition for liquid adhesives, the polymerizable monofunctional compound is preferably one that functions as a reactive diluent. The polymerizable monofunctional compound that functions as a reactive diluent can typically be used for a polymerizable monofunctional compound that is liquid at 25°C. As such a polymerizable monofunctional compound, the same one as that used to obtain the monobody of the macromonomer (a) can be used. Any one of these polymerizable monofunctional compounds may be used alone, or two or more of them may be used in combination.

The polymerizable monofunctional compound is particularly preferably selected from isodecyl (meth)acrylate, isostearyl (meth)acrylate, ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, At least one of isobutyl (meth)acrylate, isononyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, and lauryl acrylate.

<oligomer component>

The resin composition for adhesives of the present invention may further contain an oligomer component as necessary.

Examples of oligomer components include urethane-based oligomers, polyester-based oligomers, acrylic-based oligomers, polyether-based oligomers, and polyolefin-based oligomers. These may have reactive double bonds, may have functional groups and react with other components in the adhesive resin composition, or may not react with other components.

<Crosslinking agent>

The resin composition for adhesives of the present invention may further include a crosslinking agent as necessary. If the resin composition for the adhesive contains a crosslinking agent, the resin composition for the adhesive can be made hard (Cross-linking) to increase the cross-linking density of the adhesive layer. As a result, there is a tendency for the strength and retention of the adhesive layer to be more excellent. Furthermore, depending on the application, there is no need to include a crosslinking agent. In addition, when the copolymer (A) has self-crosslinking properties, for example, when it has both a hydroxyl group and an isocyanate group, sufficient strength, retention, etc. can be obtained even if a crosslinking agent is not included.

As a crosslinking agent, an isocyanate type, an epoxy type, a metal chelate type, a photocurable type, etc., a melamine type, an aziridine type etc. are mentioned, for example. Any one of these crosslinking agents may be used alone, or two or more of them may be used in combination.

Examples of the isocyanate-based crosslinking agent include aromatic polyisocyanates such as xylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and toluene diisocyanate; hexamethylene diisocyanate, isophorone Aliphatic or cycloaliphatic polyisocyanates such as diisocyanates, hydrogenated products of the aromatic polyisocyanates; dimers or trimers of these polyisocyanates; those containing these polyisocyanates and polyols such as trimethylolpropane Adducts and so on. Any one of these may be used alone, or two or more of them may be used in combination.

As the epoxy-based crosslinking agent, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A type epoxy resin, N, N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N-diglycidylaniline, N,N-diglycidyl toluidine, etc.

As the metal chelate-based crosslinking agent, a compound in which a polyvalent metal and an organic compound are covalently bonded or coordinately bonded can be cited. As the multivalent metal, for example, Examples include aluminum, nickel, chromium, copper, iron, tin, titanium, zinc, cobalt, manganese, and zirconium. Examples of the organic compound include organic compounds having oxygen atoms such as ketone compounds such as acetone, alkyl esters, alcohol compounds, carboxylic acid compounds, and ether compounds.

The photocurable crosslinking agent is a compound that undergoes a crosslinking reaction by the action of a photopolymerization initiator or the like when irradiated with actinic rays such as ultraviolet rays.

Examples of such crosslinking agents include: polymerizable polyfunctional compounds having two or more radical polymerizable groups; having two or more selected from the group consisting of isocyanate groups, epoxy groups, melamine groups, ethylene glycol groups, Polyfunctional organic resins with functional groups in the group consisting of siloxane groups and amine groups; organometallic compounds with metal complexes, etc. Examples of the metal in the metal complex include zinc, aluminum, sodium, zirconium, calcium, and the like.

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

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

<Reaction initiator>

The resin composition for adhesives of the present invention may further include a reaction initiator as necessary.

The reaction initiator is a compound that generates free radicals by irradiation with actinic rays (ultraviolet rays, etc.) or heating.

As a reaction initiator, a photopolymerization initiator, a thermal polymerization initiator, etc. are mentioned, for example.

Examples of the photopolymerization initiator include compounds that decompose by irradiation with actinic rays to generate free radicals; or, when irradiation with actinic rays, hydrogen dehydrogenates from constituent components in the formulation to generate Free radical compounds.

The photopolymerization initiator is not particularly limited, and well-known photopolymerization initiators can be suitably used. For example, benzophenone, 2-methylbenzophenone, 4-methylbenzophenone, 2 , 2-Dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- Ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-[4-( 2-Hydroxy-2-methyl-propanyl)-benzyl)phenyl)-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)- 2-morpholinopropane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl ]-1-butanone, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, double (η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 1,2-octanedione 1-[4-(phenylthio)-2-(o-benzyl oxime)], ethyl ketone 1-[9-ethyl-6-(2-methylbenzyl)-9H-carb Azol-3-yl]-1-(o-acetyloxime) and the like. Any of these photopolymerization initiators can be used alone, or Two or more types can be used in combination.

<Filling agent>

The resin composition for an adhesive of the present invention may further include a filler as necessary.

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

<Organic Solvent>

In order to improve coating suitability, film-forming properties, etc., the resin composition for adhesives of the present invention may optionally contain an organic solvent.

The organic solvent is not particularly limited as long as it can dissolve the copolymer (A). Examples include hydrocarbon solvents such as heptane, cyclohexane, toluene, xylene, octane, and mineral spirits. ; Ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate and other ester solvents; methyl ethyl ketone, methyl isobutyl Ketone solvents such as base ketone, diisobutyl ketone, cyclohexanone; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, second butanol, isobutanol; dioxane, ethylene glycol mono Ether solvents such as diethyl ether, ethylene glycol monobutyl ether, propylene glycol monopropyl ether; Swasol 310, Swasol 1000, Swasol 1500 manufactured by Cosmo Petroleum Company And other aromatic petroleum-based solvents 剂 etc. These organic solvents can be used alone or in combination of two or more.

When the resin composition for an adhesive is a resin composition for actinic ray hardening type adhesive, it is preferable that the resin composition for an adhesive contains substantially no organic solvent. The fact that the organic solvent is not contained substantially means that the content of the organic solvent is 1% by mass or less with respect to the total mass of the resin composition for adhesives. The content of the organic solvent may also be 0% by mass. The content of the organic solvent can be determined by gas chromatography.

<Other additives>

The resin composition for adhesives of the present invention may optionally contain reaction catalysts, adhesion-imparting resins, antioxidants, light stabilizers, metal deactivators, anti-aging agents, moisture absorbents, rust inhibitors, water-repellent agents, etc. additive.

Examples of the reaction catalyst include tertiary amine compounds, quaternary ammonium compounds, tin laurate compounds, and the like.

Examples of antioxidants include phenol-based, phosphorus-based, hydroxylamine-based, and sulfur-based antioxidants. Among them, in terms of less coloration of the resin after heating, phenol-based and phosphoric acid-based antioxidants are preferred. These can be used individually or in combination of multiple types. The content of the antioxidant is preferably 0.1 parts by mass to 5 parts by mass relative to 100 parts by mass of the copolymer (A).

The resin composition for adhesives of the present invention can be prepared, for example, by producing the above-mentioned copolymer (A), and, if necessary, blending other components (polymerizable monofunctional compound, cross-linking) in the obtained copolymer (A). Agent, photopolymerization initiator, etc.).

The composition of the resin composition for adhesives can be based on the use of the resin composition for adhesives. It can be set appropriately according to the way, usage pattern, etc.

<Preferred Embodiment>

As a preferable embodiment of the resin composition for adhesives of this invention, the following resin composition for adhesives (1)-resin composition for adhesives (3), etc. are mentioned.

(Resin composition for adhesives (1))

The adhesive resin composition (1) is a polymerizable monofunctional compound containing at least a copolymer (A), one radically polymerizable group, a polymerizable polyfunctional compound having two or more radically polymerizable groups, and A liquid adhesive resin composition of a photopolymerization initiator.

The resin composition (1) for an adhesive is an actinic ray hardening type.

The so-called "liquid" means that it is liquid at 25°C. The resin composition (1) for liquid adhesives preferably has a viscosity of 1,000 mPa as measured by a B-type viscometer at 25°C. s~800,000mPa. s.

The resin composition (1) for an adhesive preferably contains substantially no organic solvent.

The resin composition (1) for adhesives may further contain fillers, oligomer components, other additives, etc., if necessary.

The resin composition (1) for adhesives can be used as LOCA, for example.

In the adhesive resin composition (1), the content of the copolymer (A) is preferably 10% by mass to 80% by mass relative to the total mass (100% by mass) of the copolymer (A) and the polymerizable monofunctional compound , More preferably 15% by mass to 70% by mass. If it is more than the said lower limit and less than the upper limit, the viscosity at the time of coating or filling at the time of forming an adhesive layer will become an appropriate value, and workability will improve.

In the adhesive resin composition (1), the content of the polymerizable polyfunctional compound is preferably 0.1 to 50 parts by mass relative to the total of 100 parts by mass of the copolymer (A) and the polymerizable monofunctional compound. More preferably, it is 0.5 parts by mass to 20 parts by mass. If it is more than the said lower limit and less than the upper limit, the viscosity at the time of coating or filling at the time of forming an adhesive layer will become an appropriate value, and workability will improve.

In the adhesive resin composition (1), relative to 100 parts by mass of the copolymer (A), the content of the photopolymerization initiator is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass . If it is more than the said lower limit and less than the upper limit, the retention force or durability of an adhesive layer will improve.

(Resin composition for adhesives (2))

The resin composition for adhesives (2) is a resin composition for hot-melt adhesives containing the copolymer (A).

The adhesive resin composition (2) is solid at 25°C.

The resin composition (2) for adhesives does not substantially contain an organic solvent.

The resin composition (2) for adhesives may further contain a polymerizable monofunctional compound, a crosslinking agent, a reaction initiator, a filler, an oligomer component, other additives, etc., if necessary.

The resin composition (2) for an adhesive preferably contains a crosslinking agent. Thereby, the adhesive layer or the adhesive sheet formed of the resin composition (2) for the adhesive can be hardened (crosslinked).

The resin composition (2) for an adhesive preferably contains actinic rays containing a polymerizable polyfunctional compound having two or more radical polymerizable groups as a crosslinking agent and a photopolymerization initiator as a reaction initiator Hardening type.

The resin composition (2) for adhesives can be molded into a transparent double-sided adhesive sheet shape, and can be cross-linked as necessary and used as OCA.

In the adhesive resin composition (2), the content of the copolymer (A) relative to the total mass of the adhesive resin composition is preferably 70% by mass or more, more preferably 80% by mass or more, or 100 quality%. If it is more than the said lower limit and less than the upper limit, the durability of an adhesive layer will improve.

When the resin composition (2) for an adhesive contains a crosslinking agent, the content of the crosslinking agent in the resin composition (2) for an adhesive can be suitably set according to the kind of crosslinking agent. For example, when the crosslinking agent is the polymerizable polyfunctional compound, relative to 100 parts by mass of the copolymer (A), the content of the polymerizable polyfunctional compound is preferably 1 part by mass to 20 parts by mass, and more It is preferably 3 parts by mass to 10 parts by mass. If it is more than the said lower limit and less than the upper limit, the durability of an adhesive layer will improve.

When the adhesive resin composition (2) contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 parts by mass to 10 parts by mass relative to 100 parts by mass of the copolymer (A), and more Preferably, it is 0.5 parts by mass to 5 parts by mass. If it is more than the said lower limit and less than the upper limit, the durability of an adhesive layer will improve.

(Resin composition for adhesives (3))

The adhesive resin composition (3) is a liquid adhesive resin composition containing a copolymer (A) and an organic solvent.

The resin composition (3) for liquid adhesives preferably has a viscosity of 10 mPa as measured by a B-type viscometer at 25°C. s~800,000mPa. s, more preferably 100mPa. s~10,000mPa. s, more preferably 200mPa. s~7,000mPa. s, and more preferably 200 mPa. s~5,000mPa. s, the best is 500mPa. s~3500mPa. s. If it is more than the said lower limit and less than the upper limit, the coating property or workability at the time of coating the resin composition for liquid adhesives will improve.

The resin composition (3) for adhesives may further include a polymerizable monofunctional compound, a crosslinking agent, a reaction initiator, a filler, an oligomer component, other additives, etc., as necessary.

The resin composition (3) for an adhesive preferably contains a crosslinking agent. Thereby, the adhesive layer or the adhesive sheet formed of the resin composition (3) for the adhesive can be hardened (crosslinked).

The resin composition (3) for adhesives preferably contains actinic rays containing a polymerizable polyfunctional compound having two or more radical polymerizable groups as a crosslinking agent and a photopolymerization initiator as a reaction initiator A hardening type, or a thermosetting type containing a compound that reacts with the functional group contained in the copolymer A by heat.

The resin composition (3) for the adhesive can be formed into a transparent double-sided adhesive sheet by coating the resin composition (3) for the adhesive on a peelable substrate and drying, for example, by heating Or it can be cross-linked by ultraviolet irradiation, etc., and used as an adhesive.

In the adhesive resin composition (3), the content of the copolymer (A) relative to the solid content of the adhesive resin composition is preferably 70% by mass or more, more preferably 80% by mass or more, or 100 quality%. If it is more than the said lower limit and less than the upper limit, the durability of an adhesive layer will improve.

The solid content of the adhesive resin composition is the remainder obtained by removing the organic solvent from the adhesive resin composition (3).

The solid content concentration of the resin composition for an adhesive can be suitably set in consideration of the viscosity of the resin composition for an adhesive, etc., for example, it can be set to 10 mass%-90 mass %. From the viewpoint of productivity or environmental load reduction, the amount of organic solvent in the adhesive resin composition (3) is preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less.

When the resin composition (3) for an adhesive contains a crosslinking agent, the content of the crosslinking agent in the resin composition (3) for an adhesive can be suitably set according to the kind of crosslinking agent. For example, when the crosslinking agent is the polymerizable polyfunctional compound, the content of the polymerizable polyfunctional compound is preferably 0.1 parts by mass to 20 parts by mass relative to 100 parts by mass of the copolymer (A). It is preferably 0.5 parts by mass to 10 parts by mass. If it is more than the said lower limit and less than the upper limit, the durability of an adhesive layer will improve.

In the case where the crosslinking agent is of the thermosetting type, as the crosslinking agent, for example, isocyanate, epoxy, metal chelate, photocuring, etc., melamine, aziridine, etc. can be cited. Hardening type crosslinking agent. Specific examples of crosslinking agents such as isocyanate-based, epoxy-based, metal chelate-based, and carbodiimide-based crosslinking agents include the same ones as described above. These crosslinking agents may be used alone or in combination of two or more.

When the crosslinking agent is the thermosetting type, the copolymer (A) preferably includes 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, it is relative to the copolymer (A) 100 parts by mass, the content of the thermosetting crosslinking agent is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 3 parts by mass. If it is more than the said lower limit and less than the upper limit, the pot life (pot life) of the composition for adhesives will become good, or the durability of an adhesive layer will improve.

When the adhesive resin composition (3) contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 parts by mass to 10 parts by mass relative to 100 parts by mass of the copolymer (A), and more Preferably, it is 0.5 parts by mass to 5 parts by mass. If it is more than the said lower limit and less than the upper limit, the durability of an adhesive layer will improve.

<Use>

The resin composition for adhesives of this invention can be used for bonding of members, etc..

At the time of lamination, the resin composition for an adhesive may be pre-formed into a sheet shape or coated to form an adhesive sheet and placed between the members, or the one that is not formed into a sheet may be directly placed between the members.

The adhesive sheet will be described in detail later.

It does not specifically limit as a member to be bonded using the resin composition for adhesives of this invention. For example, it can be used for bonding of window film for vehicles, construction, etc.; bonding of labels during label display, etc.

When the adhesive resin composition is transparent, it can be processed into a transparent double-sided adhesive sheet shape and used as an OCA for the bonding of various panels in displays such as liquid crystal panels, and the bonding of transparent plates such as glass. When the resin composition for adhesives is transparent and liquid, it can be used directly as LOCA for such bonding.

The so-called "transparency" means that by following the Japanese Industrial Standards (Japanese Industrial Standards) Standard, JIS) K7361 method to measure the haze value when the thickness of the pressure-sensitive adhesive sheet is adjusted to 150 μm is 10 or less.

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

An example of the method of bonding a member using the resin composition for adhesives of (1) is shown below.

First, the adhesive resin composition of (1) is coated on the surface of the first member to form an adhesive layer, and the second member is laminated on the surface of the first member, and the second member is hardened as necessary. Thereby, a laminated body in which the first member and the second member are bonded via the adhesive layer is formed.

The application of the resin composition for an adhesive of (1) can be performed using a known wet coating method such as slit coating and spin coating. Alternatively, it may also be a method of applying a certain amount of the adhesive resin composition to bond the second member, thereby filling the adhesive resin composition between the first member and the second member.

The coating amount of the adhesive resin composition of (1) can be set according to the thickness of the adhesive layer to be formed. The thickness of the adhesive layer can be appropriately set according to the application, and is not particularly limited, but is typically about 10 μm to 500 μm.

In the case where the resin composition for the adhesive is curable, the adhesive layer (resin composition for the adhesive) may be cured before or after the lamination of the second member.

The hardening method of the adhesive layer is not particularly limited. For example, in the case where the resin composition for an adhesive contains a polyfunctional (meth)acrylate as a crosslinking agent and a photopolymerization initiator, the adhesive layer can be cured by irradiation with actinic rays such as ultraviolet rays (light hard change). When the copolymer (A) has a reactive group such as a hydroxyl group, and the resin composition for an adhesive contains a crosslinking agent (isocyanate series, etc.) that can chemically bond to the reactive group by heat, it can be used The adhesive layer is hardened by heating (thermal hardening).

In the case of photocuring the adhesive layer, as actinic rays, ultraviolet rays are preferred in terms of versatility. As a light source of ultraviolet rays, for example, a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, and the like can be cited.

In the case of thermally hardening the adhesive layer, as the heating mechanism, a well-known heating mechanism such as a drying furnace such as a hot air stove, an electric furnace, and an infrared induction heating furnace can be used. The heating temperature is not particularly limited, but is preferably about 50°C to 180°C. The heating time is not particularly limited, but is preferably about 10 seconds to 60 minutes.

Before thermal curing, in order to prevent the occurrence of defects, preheating, air blowing, etc. may be performed under heating conditions where the resin composition for adhesives does not harden substantially. The preheating can be performed at a temperature of about 30°C to 100°C for about 30 seconds to 15 minutes, for example. Blowing is usually performed by blowing air heated to a temperature of about 30°C to 100°C on the coating surface for about 30 seconds to 15 minutes.

It can also be cured after heat hardening. The curing conditions can be set to be performed at 0°C to 60°C for about 1 to 10 days, for example.

Since the resin composition for an adhesive of the present invention contains the copolymer (A), it can form an adhesive layer with sufficient holding power and adhesive power in an appropriate range, and low substrate contamination due to glue residue.

〔Adhesive sheet〕

The adhesive sheet of the present invention is an adhesive sheet using the resin composition for adhesives. That is, it is an adhesive sheet provided with the adhesive layer formed of the said resin composition for adhesives.

In the case where the resin composition for the adhesive is capable of being hardened, the adhesive sheet of the present invention may be one containing the resin composition for the adhesive, or may be a cured product containing the resin composition for the adhesive By. In terms of handling properties of the pressure-sensitive adhesive sheet, a cured product containing the resin composition for the pressure-sensitive adhesive is preferable.

The adhesive sheet of the present invention may be a transparent double-sided adhesive sheet.

The thickness of the pressure-sensitive adhesive sheet of the present invention can be appropriately set according to the application, and is not particularly limited, but is typically about 10 μm to 500 μm.

The pressure-sensitive adhesive sheet of the present invention can be formed as an pressure-sensitive adhesive sheet with a peelable base material in which a peelable base material is laminated on one or both sides of the adhesive sheet.

The adhesive sheet of the present invention can be manufactured by molding the resin composition for an adhesive into a sheet shape, and curing it as necessary.

The molding of the resin composition for adhesives can be performed by a known method. For example, when the resin composition for an adhesive of the present invention is in a solid state (for example, in the case of the resin composition (2) for an adhesive), the adhesive may be arranged between a pair of peelable substrates. The resin composition for an agent is heated from both sides of a pair of peelable base materials to melt the resin composition for an adhesive, and a method is formed into a sheet shape. When the resin composition for an adhesive of the present invention is in a liquid form (for example, in the case of the resin composition for an adhesive (1) or the resin composition for an adhesive (3)), the adhesive may be A method of applying a resin composition to a releasable base material, drying it as necessary, and molding it into a sheet shape, etc.

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

As with the resin composition for adhesives, the adhesive sheet of the present invention can be used for bonding members and the like.

For example, an adhesive sheet is arranged on the surface of the first member, and the second member is laminated on it, and hardened as necessary. Thereby, a laminated body in which the first member and the second member are bonded via the adhesive sheet is formed.

The adhesive sheet of the present invention uses the resin composition for an adhesive, and therefore has sufficient holding power and an adhesive force within an appropriate range. In addition, the substrate contamination caused by residual glue is low.

〔Protection Sheet〕

The protective sheet of the present invention is a protective sheet using the resin composition for adhesives. That is, it is a protective sheet provided with the adhesive layer formed of the said resin composition for adhesives.

In the case where the resin composition for the adhesive is capable of being hardened, the protective sheet of the present invention may be one containing the resin composition for the adhesive, or may be a cured product containing the resin composition for the adhesive By. In terms of handling properties of the protective sheet, a cured product containing the resin composition for adhesives is preferred.

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

The protective sheet of the present invention can be formed as a protective sheet with a peelable base material in which a peelable base material is laminated on one side or both sides of the protective sheet.

The protective sheet of the present invention can be manufactured in the same manner as the adhesive sheet described above.

The protective sheet of the present invention is used to protect the surface of a substrate. Typically, it fits The surface of the substrate, thereafter, peels off from the surface of the substrate when protection is not required.

The substrate protected by the protective sheet of the present invention is not particularly limited, and examples include optical components such as polarizers and front panels used in touch panel displays; parts of automobiles, motorcycles, ships, household appliances, etc.; industry Use parts, etc.

The protective sheet of the present invention uses the resin composition for the adhesive, and therefore has sufficient holding power and an appropriate range of adhesive power, and has low substrate contamination due to residual glue, so it is not easy to cause adhesion to the substrate. The peeling after the surface of the material can be easily peeled from the surface of the substrate when protection is not required.

[Example]

Hereinafter, the present invention will be described in further detail with examples, but the following examples do not limit the scope of the present invention. In the following examples, "parts" means "parts by mass".

The measurement method used in each example is shown below.

<Measurement method>

(Number average molecular weight of macromonomers)

The number average molecular weight (Mn) of the macromonomer was measured using a gel permeation chromatography (GPC) device (manufactured by Tosoh Co., Ltd., HLC-8320). Prepare a 0.2% by mass tetrahydrofuran (THF) solution of the macromonomer, and install the column (TSKgel Super HZM-M×HZM-M×HZ2000, TSK protection column (TSKgel Super) manufactured by Tosoh Corporation ( Guard column) SuperHZ-L) was injected into the device of the solution 10μL, at flow rate: 0.35mL/min, lysate: THF (stabilizer: butyl hydroxytoluene (butyl hydroxy toluene) toluene, BHT)), column temperature: Measure at 40°C, and calculate the number average molecular weight using standard polystyrene conversion.

(Weight average molecular weight of copolymer)

The weight average molecular weight (Mw) of the copolymer was measured using a GPC device (manufactured by Tosoh Co., Ltd., HLC-8120). A 0.3% by mass THF solution of the copolymer was prepared, and 20 μL of the solution was injected into the device equipped with a column (TSKgel Super HM-H×4, TSK guard column SuperH-H) manufactured by Tosoh Corporation, and the flow rate was: The measurement was performed under the conditions of 0.6 mL/min, eluate: THF (stabilizer BHT), and column temperature: 40°C, and the weight average molecular weight (Mw) was calculated by standard polystyrene conversion.

(Determination of viscosity of copolymer in 50% ethyl acetate solution)

The viscosity of a 50% ethyl acetate solution of the copolymer was measured at 25°C with a B-type rotary viscometer (B8H type) on an ethyl acetate solution with the polymer content of the copolymer set to 50%.

(Small angle X-ray scattering measurement (SAXS) of copolymers)

The small-angle X-ray scattering measurement is carried out using SPring-8 BL03XU (Frontier Soft Matter Development-Industry-University Joint Beamline), which is a large-scale radiographic equipment.

The copolymer solution obtained in each example was coated on a 50μm peeling PET film using a 500μm applicator, dried at 90°C for 90 minutes to form a copolymer layer, and a 50μm peeling PET film was pasted thereon, As a result, a laminated sheet having a constitution of peeling PET film-adhesive layer-peeling PET film was obtained. PET stands for polyethylene terephthalate Diester (polyethylene terephthalate), "peeling" before the PET film means peeling treatment, and the value (μm) before the PET film means the thickness of the PET film (the same applies below).

One of the laminated sheets was peeled off the PET film to expose the copolymer layer, and the laminate was attached to the sample jig. After that, the remaining peeling PET film was peeled off, and it was set as the state which installed only the copolymer layer in the jig|tool for a sample. The copolymer layer was used as a sample, and a two-dimensional scattering image of the sample was obtained by the following procedure.

The beam shape of X-rays was adjusted to 120 μm in length and 120 μm in width. The X-ray wavelength is set to 1 Å, and the detector uses a Charge Coupled Device (CCD) (Hamamatsu Photonics (Hamamatsu Photonics) V7739P+ORCA R2). The camera length was set to about 4m, and a standard sample (collagen) was used for correction. Adjust the type or thickness of the attenuator (attenuator), and the exposure time, and irradiate the sample with X-rays on the basis that the detector will not be damaged by strong X-rays to obtain a two-dimensional scattering image of the sample .

The background is corrected based on the two-dimensional scattering image of the sample obtained by the procedure. Specifically, the two-dimensional scattering image of the background obtained by performing the same operation as the above procedure without the sample is acquired, and the background is subtracted from the two-dimensional scattering image of the sample using image processing software (Image-J) Obtain the two-dimensional scattering image for analysis. Ring-shaped scattering was confirmed in the two-dimensional scattering image for analysis.

Secondly, the two-dimensional scattering image for self-analysis is converted into a one-dimensional scattering spectrum. Specifically, the X-ray data processing software (Fit2d) is used to read the two-dimensional scattering image for analysis and integrate all the azimuth angles to obtain the horizontal axis as q[nm ^-1 ] and the vertical axis. The axis is set to the one-dimensional scattering spectrum of the scattering intensity. The range of q (analysis target area) is set to 0.04 to 0.4. In the one-dimensional scattering spectrum, the peak is confirmed between q=0.2~0.4.

According to the obtained one-dimensional scattering distribution, the half-value width X of the one-dimensional scattering peak and the peak position Y of the one-dimensional scattering distribution are obtained.

In the one-dimensional scattering distribution, there are cases where the minimum value is obtained near q=0.1 and the scattering intensity becomes higher toward the origin, and the case where the scattering intensity decreases toward the origin after passing the inflection point near q=0.1. When a minimum value is obtained in the vicinity of q=0.1 and the scattering intensity becomes higher toward the origin, the area of q that is larger than the minimum value is used as an analysis target. When the scattering intensity decreases toward the origin after passing the inflection point in the vicinity of q=0.1, the area of q larger than the inflection point is taken as the analysis target. Next, as a baseline correction, the minimum value of the scattering intensity of the analysis target area is obtained, and the minimum value is subtracted from all areas to perform baseline correction. Regarding the obtained corrected one-dimensional scattering distribution, the Gauss function and the Lorentz function are used for fitting, and the half-value width (half width) of the obtained composite function is set to X , Set the peak position to Y. Use the waveform separation software (Fityk) when fitting.

<Synthesis Example 1>

(Manufacturing of Dispersant 1)

Add 900 parts of deionized water, 60 parts of 2-sulfoethyl sodium methacrylate, 10 parts of potassium methacrylate, and 12 parts of methyl methacrylate to a polymerization device equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube. Methyl methacrylate (Methyl methacrylate, MMA) and stirring, while replacing the inside of the polymerization device with nitrogen, the temperature was raised to 50°C. 0.08 parts of 2,2'-azobis(2-methylpropionamidine) dihydrochloride as a polymerization initiator was added thereto, and the temperature was further increased to 60°C. After the temperature was raised, a drip pump was used to continuously drip MMA for 75 minutes at a rate of 0.24 parts/min.

After keeping the reaction solution at 60° C. for 6 hours, it was cooled to room temperature to obtain Dispersant 1 having a solid content of 10% by mass as a transparent aqueous solution.

(Manufacturing of chain transfer agent 1)

In a nitrogen environment, add 1.00 g of cobalt (II) acetate tetrahydrate and 1.93 g of diphenylglyoxime, and 80 mL of diethyl ether that has been deoxygenated by nitrogen bubbling in a synthesis device equipped with a stirring device. Stir at low temperature for 30 minutes. Then, 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, thereby obtaining 2.12 g of chain transfer agent 1 as a russet solid.

(Manufacturing of Giant Monomers)

Add 145 parts of deionized water, 0.1 parts of sodium sulfate, and 0.25 parts of Dispersant 1 (solid content 10% by mass) to a polymerization device equipped with a mixer, a cooling tube, a thermometer, and a nitrogen introduction tube, and stir to make uniform Aqueous solution. Next, add 100 parts of MMA, 0.0035 parts of chain transfer agent 1 and 0.4 parts of Perocta (registered trademark) O(1,1,3,3-tetramethylbutyl peroxide) as a polymerization initiator. Oxygen 2-ethylhexanoate (manufactured by Nippon Oil & Fat Co., Ltd.), and made into an aqueous suspension.

Next, the inside of the polymerization apparatus was replaced with nitrogen and the temperature was raised to 80°C to react for 3.5 hours, and in order to increase the polymerization rate, the temperature was raised to 90°C and maintained for 1 hour. Afterwards, The reaction liquid was cooled to 40°C to obtain an aqueous suspension containing macromonomers. The aqueous suspension is filtered with a filter, the residue remaining on the filter is washed with deionized water, dehydrated, and dried at 40° C. for 16 hours to obtain the macromonomer (a-1). The number average molecular weight of this macromonomer (a-1) is 3,000.

<Synthesis Example 2>

In the synthesis example 1 (manufacturing of the macromonomer), the addition amount of Perocta O and the chain transfer agent 1 was set as shown in Table 1. Except for this, it was obtained in the same manner as in the synthesis example 1. Giant monomer (a-2). The number average molecular weight of this macromonomer (a-2) was 6,700.

<Manufacturing Example 1>

In a four-necked flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen inlet, 40 parts of ethyl acetate and 8 parts of isopropanol (IPA) were added as the initial addition solvent as the initial addition monomer 10 parts of macromonomer (a-1) and 5 parts of lauryl acrylate (LA) are added, and the external temperature is increased to 85°C under nitrogen aeration. After the external temperature reached 85°C and the internal temperature was stable, 20 parts of ethyl acetate, 84.5 parts of LA, 0.5 parts of acrylic acid, and 0.13 parts of Nyper BMT as a polymerization initiator were added dropwise over 4 hours. -A mixture of K40 (manufactured by NOF, trade name, benzyl peroxide) (dropwise addition). After maintaining for 1 hour after the end of the dropping, a mixture containing 0.5 parts of Perocta O and 10 parts of ethyl acetate was added over 1 hour. Thereafter, after maintaining for 2 hours, 0.5 part of antioxidant (manufactured by BASF, trade name "Irganox (registered trademark) 1010") was added, and the solid content ((monomer + Solvent addition) After adding ethyl acetate so that the monomer addition amount ratio) became 50%, it cooled to room temperature and obtained the copolymer solution (A-1).

The weight average molecular weight (Mw) of the copolymer in the copolymer solution (A-1), the half-value width X of the one-dimensional scattering peak in the small-angle X-ray scattering measurement (SAXS) and the peak position Y of the one-dimensional scattering distribution, The viscosity of the 50% ethyl acetate solution is shown in Table 2.

<Manufacturing Example 2~Manufacturing Example 9>

As shown in Table 2, change the solvent (dropping solvent) and monomer (dropping single weight) in the mixture of initial addition of solvent, initial addition of monomer, and dropwise addition after heating. The copolymer solution (A-2) to the copolymer solution (A-9) were obtained in the same manner as in Example 1.

The weight average molecular weight (Mw) of the copolymer in the copolymer solution obtained in each example, the half-value width X of the one-dimensional scattering peak in the small-angle X-ray scattering measurement (SAXS) and the peak position Y of the one-dimensional scattering distribution are shown. In Table 2.

<Example 1>

80 parts of the copolymer solution (A-1) was desolvated so that the solid content became 99% or more, 60 parts of isodecyl acrylate (IDAA), crosslinking agent (PETA: Shinnakamura Chemical, trade name "NK Ester (NK Ester) TMM-3L", pentaerythritol triacrylate) 10 parts, and photopolymerization initiator (manufactured by BASF, trade name "IRGACURE (registered trademark) 184", 1-hydroxy 3 parts of cyclohexyl phenyl ketone) were mixed to prepare a liquid adhesive resin composition.

Regarding the obtained resin composition for an adhesive, an adhesive sheet was produced according to the following procedure. Regarding the adhesive sheet, the adhesive force, retention force, and resistance to substrate staining were determined according to the following procedure Dyeability was evaluated. The results are shown in Table 3.

(Making of Adhesive Sheet)

On the peeling polyethylene terephthalate (PET) film, apply the adhesive resin composition with an applicator so that the thickness of the adhesive layer becomes 50μm, and paste the 50μm peeling PET film on the adhesive surface, and Ultraviolet rays (UV) were irradiated under the following conditions to harden the adhesive layer, thereby obtaining an adhesive sheet having a composition of peeling PET film-adhesive layer-peeling PET film. The peeling PET film refers to a PET film that has been peeled off.

"Irradiation conditions"

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

(Adhesion)

One of the adhesive sheets was peeled off the PET film, and a 38μm PET film was bonded instead to obtain a laminate. The laminate was cut into a strip with a width of 25mm and a length of 300mm, and another peeled PET film was torn off to expose the adhesive layer, and a 2kg hand roller was used so that the bonding surface became 25mm×120mm. It is bonded to a glass plate, and the peel strength (N/25mm) to the glass plate is measured at a peeling angle of 180° and a tensile speed of 300 mm/min in accordance with JIS Z 0237 to determine the adhesive force.

A: The adhesive force is 2N/25mm or less.

B: The adhesive force is greater than 2N/25mm and 3N/25mm or less.

C: The adhesive force is greater than 3N/25mm.

(Retentivity)

One of the adhesive sheets was peeled off the PET film, and instead, a 2kg hand roller was used to crimp the 38μm PET film to obtain a laminate. The laminate was cut into a strip of 25mm×100mm, and another peeled PET film was torn off. Using a 2kg hand roller, the laminate was horizontally bonded to a 30mm×100mm stainless steel (SUS )plate. According to JIS Z 0237, after curing at 40°C for 30 minutes, a weight of 1 kg was placed on the front of the PET film, and the holding time was measured with a constant temperature layer of 40°C. The retention force is judged according to the following criteria.

A: The holding time is more than 100 minutes.

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

C: The retention time is less than 60 minutes.

(Resistance to substrate contamination)

One of the adhesive sheets was peeled off the PET film, and a 38μm PET film was bonded instead to obtain a laminate. Cut the laminate into a strip with a width of 25mm and a length of 300mm, and tear off the other peeling PET film to expose the adhesive layer, and use a 2kg hand roller to bond it to 30mm so that the bonding surface becomes 25mm×12mm. ×150mm SUS board, allowed to stand at 60°C for 2 weeks. After that, the adhesive sheet was torn off under the same conditions as the adhesive force test, the SUS surface was visually observed, and the substrate contamination resistance was judged based on the following criteria.

A: No residual glue.

B: There is residual glue.

<Example 2>

Change the copolymers used to those listed in Table 3. In addition to the actual In the same manner as in Example 1, a resin composition for an adhesive was prepared, and an adhesive sheet was produced, and the adhesion, retention, and resistance to substrate contamination were evaluated.

<Example 3>

The copolymer used was changed to the one described in Table 3, except that the resin composition for an adhesive was prepared in the same manner as in Example 1, and an adhesive sheet was produced by the following method, which was the same as in Example 1. The method evaluates the adhesion, retention, and resistance to substrate contamination.

(Making of Adhesive Sheet)

After sandwiching the resin composition for the adhesive with a peeling PET film, forming an adhesive layer with a thickness of 100 μm by hot pressing at 100°C to obtain a laminate sheet consisting of peeling PET film-adhesive layer-peeling PET film, the following is The conditions are irradiated with ultraviolet (UV) to harden the adhesive layer, thereby obtaining an adhesive sheet composed of peeling PET film-adhesive layer-peeling PET film.

"Irradiation conditions"

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

<Example 4>

200 parts of the copolymer solution (A-3) and 0.24 parts of polyisocyanate ("Coronate L", manufactured by Tosoh Corporation, trade name) (PIC) were mixed to prepare a resin composition for an adhesive.

Regarding the obtained resin composition for an adhesive, an adhesive sheet was produced by the following procedure. With regard to the adhesive sheet, the adhesive force, retention force, and The resistance to substrate contamination was evaluated.

(Making of Adhesive Sheet)

On the peeling PET film, apply the adhesive resin composition with an applicator so that the thickness of the adhesive layer becomes 20μm, heat at 120°C for 1 hour to harden the adhesive layer, and then paste the peeled PET film on the adhesive surface , And curing at 50°C for 3 days to obtain an adhesive sheet composed of peeling PET film-adhesive layer-peeling PET film.

<Example 5 to Example 9, Comparative Example 1, Comparative Example 2>

The type of the copolymer solution was set as shown in Table 3. Except for this, the adhesive resin composition was prepared in the same manner as in Example 6, and an adhesive sheet was produced, which was effective in adhesion, retention, and resistance to substrate contamination. Evaluation. The results are shown in Table 3.

[Table 2]

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.

2-HEA: 2-hydroxyethyl acrylate.

IPA: Isopropanol.

PETA: pentaerythritol triacrylate (New Nakamura Chemical, trade name "NK Ester (NK Ester) TMM-3L").

Irg184: IRGACURE 184 (manufactured by BASF, trade name).

PIC: Polyisocyanate ("Coronate L", manufactured by Tosoh Corporation, trade name).

Al(acac) ₃ : Aluminum trisacetylacetonate.

The adhesive layer of Example 1 to Example 9 has appropriate adhesive force and sufficient retention force, and the substrate contamination caused by residual glue is low.

The adhesive layer of Comparative Example 1 using a copolymer having a half-value width X exceeding 0.12 had too high adhesive force and poor releasability.

The adhesive layer of Comparative Example 2 using a copolymer that does not have a one-dimensional scattering peak in the small-angle X-ray scattering measurement (SAXS) and does not have a half-value width X has poor retention. In addition, substrate contamination caused by residual glue can be observed. It is believed that the reason for the absence of a one-dimensional scattering peak is that no phase separation occurs.

[Industrial availability]

According to the present invention, it is possible to provide a resin composition for an adhesive and an adhesive sheet that can form an adhesive layer with sufficient holding power and an appropriate range of adhesive power and low substrate contamination due to glue residue.

Claims (9)

A resin composition for an adhesive, comprising: a (meth)acrylic copolymer (A) having a structural unit derived from a macromonomer (a) and a structural unit derived from a vinyl monomer (b); and The isocyanate-based crosslinking agent, with respect to the macromonomer (a), has two or more structural units represented by the following formula (a') and is represented by the following formula (1),

The vinyl monomer (b) contains an alkyl (meth)acrylic acid alkyl ester (b1) with a carbon number of 9 or more, and the (meth)acrylic copolymer (A) has a small angle X The half-value width X of the primary peak measured by the ray scattering measurement satisfies the following formula (i): 0<X≦0.12‧‧‧(i) (where R ¹ represents a hydrogen atom, a methyl group or CH ₂ OH, R ² represents OR ³ , halogen atom, COR ⁴ , COOR ⁵ , CN, CONR ⁶ R ⁷ , NHCOR ⁸ or R ⁹ , R ³ to R ⁸ each independently represent a hydrogen atom, unsubstituted or substituted alkane Group, unsubstituted or substituted alicyclic group, unsubstituted or substituted aryl group, unsubstituted or substituted heteroaryl group, unsubstituted or substituted group Non-aromatic heterocyclic group, unsubstituted or substituted aralkyl group, unsubstituted or substituted alkaryl group, unsubstituted or substituted organosilyl group, unsubstituted (Poly)organosiloxane alkyl groups with or with substituents, the substituents in these groups are selected from alkyl groups, aryl groups, heteroaryl groups, non-aromatic heterocyclic groups, aralkyl groups, and alkaryl groups. Group, carboxylic acid group (COOH), carboxylate group, epoxy group, hydroxyl group, alkoxy group, primary amine group, secondary amine group, tertiary amine group, isocyanate group, sulfonic acid group (SO ₃ H ) And at least one of the group consisting of halogen atoms, R ⁹ represents an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted The non-aromatic heterocyclic groups of these groups are selected from the group consisting of alkyl, aryl, heteroaryl, non-aromatic heterocyclic groups, aralkyl groups, alkaryl groups, and carboxylic acid groups. , Carboxylate group, epoxy group, hydroxyl group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, isocyanate group, sulfonic acid group, unsubstituted or substituted alkyl group , At least one of an unsubstituted or substituted aryl group, an unsubstituted or substituted alkene group and a halogen atom; R represents a hydrogen atom, unsubstituted or substituted The alkyl group, unsubstituted or substituted alicyclic group, unsubstituted or substituted aryl group, unsubstituted or substituted heteroaryl group, unsubstituted or substituted Non-aromatic heterocyclic group, unsubstituted or substituted aralkyl group, unsubstituted or substituted alkaryl group, unsubstituted or substituted organosilyl group, or In the unsubstituted or substituted (poly)organosiloxyalkyl group, Q represents a main chain part including two or more structural units (a'), and Z represents a terminal group). The resin composition for adhesives according to the first item of the patent application, wherein the weight average molecular weight of the (meth)acrylic copolymer (A) is 1,000 to 1,000,000. The resin composition for adhesives as described in item 1 or item 2 of the scope of patent application, wherein the content of the structural unit derived from the macromonomer (a) is 3% by mass relative to the total mass of all the structural units ~60% by mass. The resin composition for adhesives as described in item 1 or item 2 of the scope of patent application, wherein the number average molecular weight of the macromonomer (a) is 100 or more and 100,000 or less. The resin composition for adhesives according to item 1 or item 2 of the scope of patent application, wherein the (meth)acrylic copolymer (A) satisfies the condition of formula (ii): 0.1≦X/Y≦0.50 ‧‧‧‧(Ii) (X represents the half-value width of the primary peak measured by small-angle X-ray scattering, and Y represents the peak position of the one-dimensional scattering distribution). The resin composition for adhesives as described in item 1 or item 2 of the scope of patent application, wherein the Tga of the macromonomer (a) and the polymer obtained by polymerizing the vinyl monomer (b) The TgB satisfies the relationship of formula (4): Tga-TgB>0℃‧‧‧(4). The resin composition for adhesives as described in item 1 or item 2 of the scope of the patent application, wherein the solubility parameter δa of the structural unit derived from the macromonomer (a) and the monomer derived from the vinyl monomer The solubility parameter δb of the structural unit of (b) satisfies the relationship of formula (5): δa-δb>0‧‧‧(5). The resin composition for adhesives as described in item 1 or item 2 of the scope of patent application, wherein the solution viscosity when the (meth)acrylic copolymer (A) is made into a 50% ethyl acetate solution is 10 mPa . s~800,000mPa. s. An adhesive sheet that uses the resin composition for adhesives as described in any one of items 1 to 8 in the scope of the patent application.