JP2003277705A - Pressure-sensitive adhesive film for surface protection - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive film excellent in anchoring property and tackiness and causing no adhesive deposit even after long term preservation. <P>SOLUTION: The pressure-sensitive adhesive film for surface protection is obtained by forming on a resin film a tackifier layer comprising a composition containing a modified block copolymer of a vinylaromatic hydrocarbon having a specified functional group and a conjugated diene or a hydrogenated product thereof and a tackifier. The pressure-sensitive adhesive film for surface protection is alternatively obtained by forming on a resin film a tackifier layer comprising a composition containing a modified block copolymer of a vinylaromatic hydrocarbon having a specified functional group and a conjugated diene, a tackifier and a specified cross-linking agent having a specified functional group. The pressure-sensitive adhesive film for surface protection is further alternatively obtained by forming on a resin film a tackifier layer comprising a composition containing a secondary modified block copolymer obtained by reacting a cross-linking agent having specified functional group with a modified block copolymer of a vinylaromatic hydrocarbon having a specified functional group and a conjugated diene, and a tackifier. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is releasably adhered to the surface of a plate-like article such as a metal plate, a glass plate, a synthetic resin plate, etc., and the surface of these plate-like articles is scratched or dust is attached. The present invention relates to an adhesive film for surface protection that prevents More specifically, the present invention relates to a pressure-sensitive adhesive film for surface protection, which has a little change with time in the adhesive force even if it is adhered to a plate-like article and left for a relatively long time, and can maintain the adhesive force such that it can be easily peeled at all times. is there.

[0002]

2. Description of the Related Art Conventionally, as a pressure-sensitive adhesive for a surface protective pressure-sensitive adhesive film, an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive mainly composed of rubber such as natural rubber or polyisobutylene has been mainly used. The method of applying the agent to the support film has heretofore been a method of applying an adhesive solution in which an adhesive is dissolved in a solvent to the support film using a means such as roll or spray. However, the use of such a solvent has many problems such as air pollution, fire, safety and hygiene at the time of production, and economical efficiency, and the hot-melt type which does not use the solvent is becoming common. As one of the influential manufacturing means, a method of co-extruding a pressure-sensitive adhesive layer and a support film has been studied,
As for the pressure sensitive adhesive, the hot melt type pressure sensitive adhesive tends to be preferred.

However, in this co-extrusion method, the adhesive force (anchoring force) between the support film and the pressure-sensitive adhesive layer is increased.
It is difficult to perform corona treatment, alkali treatment, flame treatment and the like, which are effective means for increasing the temperature, and it is difficult to obtain a co-extruded film having good anchoring property. Therefore, when the film is attached to a metal plate or the like, since the anchoring force is small, there is a problem that interface peeling occurs between the support film and the pressure-sensitive adhesive layer, and adhesive residue occurs. Therefore, in order to solve this problem, for example, Japanese Patent Laid-Open No. 8-73699.
In the publication, a block mainly composed of a vinyl aromatic compound and a block mainly composed of a conjugated diene are used. A part of the double bond of the conjugated diene part is hydrogenated and a part of the remaining double bond is partly hydrogenated. Adhesive compositions composed of epoxidized epoxy-modified hydrogenated block copolymers have been proposed, but these have excellent anchoring power, but gelation and deterioration due to heating and long-term storage are severe and stable. I have a sex problem.

Further, when an olefin resin film, which is a representative of difficult-to-adhere materials, is used as the support film, a copolymer having ethylene as a main component, which has a high affinity with the olefin resin film, such as EVA, is adhered. A co-extrusion film as an agent layer has been proposed. However, for those having a very low vinyl acetate content, there is a problem that a sufficient anchoring force can be obtained, but there is almost no tackiness, and a high tackiness cannot be obtained. Also, for example, Japanese Patent Publication No. 7-116
No. 410 discloses that an adhesive layer using an ABA (A is a styrene polymer block and B is an ethylene / butylene copolymer block) block copolymer is formed on an olefin resin film. An adhesive film for surface protection is disclosed.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a surface protective film which is excellent in anchoring property and tackiness and does not cause adhesive residue even when stored for a long period of time.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a block copolymer having a specific functional group, and further a specific functional group. By using as a pressure-sensitive adhesive a composition in which a cross-linking agent having a specific functional group is added to the block copolymer provided with, excellent anchoring property and tackiness, no adhesive residue occurs even after long-term storage, and The inventors have found that a surface protective film that can be produced by coextrusion can be obtained, and completed the present invention. That is, the present invention is as follows.

1. (1) Functional group-containing modifier at the living end of a block copolymer composed of at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene Is added to the modified block copolymer or a hydrogenated product thereof in an amount of 100 parts by mass, and (2) a tackifier in an amount of 3 to 200 parts by mass, which is formed on a resin film. Adhesive film for surface protection.

2. (1) Functional group-containing modifier at the living end of a block copolymer composed of at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene 100 parts by mass of a modified block copolymer or a hydrogenated product thereof obtained by the addition reaction of (2) a tackifier, 3 to 200 parts by mass, and (3) a crosslinker reactive with the functional group part of the component (1). An adhesive layer containing 0.01 to 20 parts by mass of the agent,
Adhesive film for surface protection formed on a resin film.

3. (1 ′) Functional group-containing modification at the living end of a block copolymer composed of at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene A cross-linking agent having reactivity with the functional group bonded to the component (1) is added to the modified block copolymer or hydrogenated product (1) thereof obtained by the addition reaction of the agent in an amount of 0. 3-
A pressure-sensitive adhesive film for surface protection, which is obtained by forming a pressure-sensitive adhesive layer containing 100 parts by mass of a secondary modified block copolymer reacted with 10 mol and (2) a tackifier of 3 to 200 parts by mass on a resin film. .

4. The modified block copolymer or its hydrogenated product (1) is bonded to an atomic group having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group, or a modified block copolymer thereof. The pressure-sensitive adhesive film for surface protection according to any one of 1 to 3 above, which is a hydrogenated product.

5. A functional group-containing modifier is a hydroxyl group, an epoxy group, an amino group, a silanol group, in the block copolymer by an addition reaction with the living end of the block copolymer,
5. The surface protection according to any one of 1 to 4, which is a modifier having a functional group that forms a modified block copolymer having an atomic group having a functional group selected from an alkoxysilane group bonded thereto or a hydrogenated product thereof. Adhesive film.

6. The pressure-sensitive adhesive film for surface protection according to any one of 2 to 5 above, wherein the crosslinking agent is a crosslinking agent having a functional group selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group and an alkoxysilane group.

7. The modified block copolymer or its hydrogenated product (1) has at least one atomic group having a functional group selected from the following formulas (1) to (14) bonded to the modified block copolymer or its water. The pressure-sensitive adhesive film for surface protection according to any one of 1 to 6 above, which is an accessory.

[0014]

[Chemical 2] (In the above formula, R ^{1 to} R ⁴ are hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a carbon group having 1 to 24 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. A hydrogen group, R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group, where R ^{1 to} R ⁴ hydrocarbon group, and the hydrocarbon chain of R ^5, hydroxyl, epoxy group, a silanol group, in bonding mode other than alkoxysilane groups, oxygen, nitrogen, may be bonded silicon .R ⁶ is Hydrogen or an alkyl group having 1 to 8 carbon atoms.)

8. The pressure-sensitive adhesive film for surface protection according to any one of 1 to 7 above, wherein the resin film is a resin film made of a nonpolar resin.

9. The pressure-sensitive adhesive film for surface protection according to any one of 1 to 7 above, wherein the resin film is a resin film made of a polar resin.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The vinyl aromatic hydrocarbon content of the modified block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene used in the present invention or a hydrogenated product thereof is preferably 5 to 95 wt% from the balance of adhesive strength and holding power, More preferably 1
It can be used in the range of 0 to 90 wt%, more preferably 15 to 85 wt%. When the vinyl aromatic hydrocarbon content of the modified block copolymer or its hydrogenated product is 60 wt% or more, preferably 65 wt% or more, it has resin-like properties, and 6
If it is less than 0 wt%, preferably 55 wt% or less, it has elastic properties. The vinyl aromatic hydrocarbon content of the modified block copolymer or hydrogenated product thereof particularly preferred in the present invention is such that the vinyl aromatic hydrocarbon content is 5 wt% or more and less than 60 wt%, preferably 10 to 50 wt%, It is preferably 15 to 45 wt%.

Examples of the method for producing the block copolymer include, for example, JP-B-36-19286 and JP-B-43-17.
979, JP-B-46-32415, JP-B-49-36957, JP-B-48-2423, JP-B-48-4106, and JP-B-56-289.
25, JP-B-51-49567, JP-A-5
The methods described in JP-A No. 9-166518, JP-A No. 60-186577 and the like can be mentioned. The functional group-containing block copolymer used in the present invention can be obtained by addition-reacting a modifying agent described below to the living terminal of the block copolymer obtained by these methods, for example, as represented by the following general formula. Have a structure.

(AB) _n- X, A- (BA) _n- X, B- (AB) _n- X, X- (AB) _n , X- (AB) _n- X, X-A- (B-A) _n- X, X-B- (A-B) _n- X, [(B-A) _n ] _m- X, [(A-B) _n ]. _m- X, [(BA) _n- B] _m- X, [(AB) _n- A] _m- X (In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbons. And B is a polymer block mainly composed of a conjugated diene.The boundary between the A block and the B block does not necessarily need to be clearly distinguished, and n is 1
It is the above integer, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably 2 to 11. X represents a modifier residue to which an atomic group having a functional group described later is bonded. When X is added by the metallation reaction described later, it is bonded to the side chain of the A block and / or the B block. The structures of the polymer chains bonded to X may be the same or different. )

In the above description, the polymer block A containing vinyl aromatic hydrocarbon as a main component is preferably 50 wt% or more of vinyl aromatic hydrocarbon, more preferably 70 w.
A copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene containing t% or more and / or a vinyl aromatic hydrocarbon homopolymer block is shown, and a polymer block B mainly composed of a conjugated diene is preferably a conjugated diene. Represents a copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon and / or a conjugated diene homopolymer block, which is contained in an amount of more than 50 wt%, more preferably 60 wt% or more. The vinyl aromatic hydrocarbon in the copolymer block may be distributed uniformly or in a taper shape. Further, the copolymer portion may coexist with a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and / or a plurality of portions in which taper distribution is formed. The block copolymer used in the present invention may be any mixture of the block copolymers represented by the above general formula.

In the present invention, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene portion in the block copolymer can be arbitrarily changed by using a polar compound described later, and the conjugated diene can be When 3-butadiene is used, the 1,2-vinyl bond content is preferably 5 to 90%, more preferably 10 to 80%. When isoprene is used as the conjugated diene or 1,3-butadiene and isoprene are combined. When used in combination, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is preferably 3-8.
It is 0%, more preferably 5 to 70%. However, when the hydrogenated product is used as the block copolymer, the 1,2-vinyl bond content is preferably 10 to 80 when the 1,3-butadiene is used as the conjugated diene.
%, And more preferably 25 to 75%, and when isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used in combination, the 1,2-vinyl bond and the 3,4-vinyl bond are The total amount is preferably 5 to 70
% Is recommended. In the present invention,
The total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, the amount of 1,2-vinyl bonds when 1,3-butadiene is used as the conjugated diene) is hereinafter referred to as the vinyl bond amount.

In the present invention, the conjugated diene is a diolefin having a pair of conjugated double bonds, for example, 1,3
-Butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, 1,3-hexadiene and the like, but particularly common ones are 1,3-butadiene,
Examples include isoprene. These may be used not only in one kind but also in two or more kinds in the production of one block copolymer.

As the vinyl aromatic hydrocarbon, styrene, o-methylstyrene, p-methylstyrene, p
There are -tert-butyl styrene, 1,3-dimethyl styrene, α-methyl styrene, vinyl naphthalene, vinyl anthracene and the like, but styrene is particularly common. These may be used not only in one kind but also in two or more kinds in the production of one block copolymer.

In the present invention, when isoprene and 1,3-butadiene are used together as the conjugated diene of the block copolymer, the mass ratio of isoprene and 1,3-butadiene is preferably 95/5 to 5/95, more preferably Is 90/1
0-10 / 90, more preferably 85 / 15-15 / 8
It is 5. In particular, when obtaining a pressure-sensitive adhesive composition excellent in low-temperature characteristics, the mass ratio of isoprene and 1,3-butadiene is preferably 49/51 to 5/95, more preferably 45.
/ 55 to 10/90, more preferably 40/60 to 15
/ 85 is recommended. Isoprene and 1,3-
When butadiene is used in combination, a composition having good viscosity stability and appearance characteristics can be obtained even in melt kneading at high temperature or coextrusion.

In the present invention, in order to enhance the compatibility with the tackifier, the ratio of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer (referred to as the vinyl aromatic hydrocarbon block ratio) is determined. Can be adjusted,
The block ratio of vinyl aromatic hydrocarbons is preferably 50 w
It can be adjusted to t% or more, more preferably 50 wt% to 98 wt%, and further preferably 60 to 97 wt%. The block ratio of the vinyl aromatic hydrocarbon incorporated in the block copolymer is measured by oxidative decomposition of the block copolymer with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IMK.
OLTHOFF, et al. J. Polym. Sc
i. 1,429 (1946)), the content of the vinyl aromatic hydrocarbon polymer block component (excluding the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less). Can be obtained from the following equation. Block ratio of vinyl aromatic hydrocarbon (%) = (mass of vinyl aromatic hydrocarbon polymer block in block copolymer / mass of all vinyl aromatic hydrocarbon in block copolymer) × 100

In the present invention, as the solvent used for producing the block copolymer, butane, pentane, hexane, isopentane, heptane, octane, isooctane and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, methyl are used. Alicyclic hydrocarbons such as cyclohexane and ethylcyclohexane, or hydrocarbon solvents such as aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or as a mixture of two or more.

Further, an organolithium compound is preferably used for the production of the block copolymer, and the organolithium compound used is a compound having one or more lithium atoms bonded in the molecule, such as ethyllithium, n-
Examples thereof include propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldilithium and isoprenyldilithium.
These may be used alone or as a mixture of two or more. Further, the organolithium compound may be added in one or more divided portions during the polymerization in the production of the block copolymer.

In the present invention, for the purpose of adjusting the polymerization rate during the production of the block copolymer, changing the microstructure of the polymerized conjugated diene portion, adjusting the reactivity ratio of the conjugated diene and the vinyl aromatic hydrocarbon, etc. Compounds and randomizers can be used. Examples of polar compounds and randomizing agents include ethers, amines, thioethers, phosphines and phosphoramides, potassium or sodium salts of alkylbenzenesulfonic acid, and alkoxides of potassium or sodium. Examples of suitable ethers are dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether. As amines, tertiary amine, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines can be used. Examples of the phosphine and phosphoramide include triphenylphosphine and hexamethylphosphoramide.

In the present invention, the polymerization temperature for producing the block copolymer is preferably -10 ° C to 150 ° C.
More preferably, it is 30 ° C to 120 ° C. The time required for the polymerization varies depending on the conditions, but it is preferably within 48 hours, particularly preferably 0.5 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within the range of the above-mentioned polymerization temperature and is a pressure sufficient to maintain the monomer and the solvent in the liquid phase. Further, it is preferable that impurities such as water, oxygen, carbon dioxide gas, etc. which inactivate the catalyst and the living polymer are not mixed in the polymerization system.

The modified block copolymer or hydrogenated product (1) thereof used in the present invention comprises at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block A mainly composed of conjugated diene. A functional group-containing modifier is added to the living end of the block copolymer consisting of the polymer block B, and a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, Acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino Group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate Group, a silanol group, an alkoxysilane group, a silicon halide group, a tin halide group, an alkoxytin group, a modified block copolymer having an atomic group having at least one functional group selected from a phenyltin group bonded thereto, or The hydrogenated product.

A method for obtaining a block copolymer having an atomic group having such a functional group bonded thereto or a hydrogenated product thereof is as follows. A modified block copolymer having an atomic group having a functional group selected from a functional group bonded thereto or a functional group-forming modifier that forms a hydrogenated product thereof, or an atomic group obtained by protecting the functional group by a known method is used. It can be obtained by a method in which a binding modifier is bound.
As another method, a block copolymer is reacted with an organic alkali metal compound such as an organolithium compound (metalation reaction), and the above modifier is added to a polymer obtained by adding an organic alkali metal to the block copolymer. There is a method of making it. In the latter case, the hydrogenation product of the block copolymer may be obtained and then a metalation reaction may be carried out to react the above-mentioned modifier. Depending on the type of modifier, the hydroxyl group, amino group, etc. may generally be an organic metal salt at the stage of reaction with the modifier, in which case it should be treated with a compound having active hydrogen such as water or alcohol. Thus, a hydroxyl group or an amino group can be obtained. In the present invention, when the living terminal of the block copolymer is reacted with the modifier, a partially unmodified block copolymer may be mixed in the modified block copolymer of the component (1). . The proportion of the unmodified block copolymer mixed in the modified block copolymer of the component (1) is preferably 70 wt% or less,
More preferably 60 wt% or less, still more preferably 50 w
It is recommended to be t% or less.

In the pressure-sensitive adhesive film for surface protection of the present invention, since the atomic group bonded to the modified block copolymer or its hydrogenated product has a functional group selected from the above-mentioned functional groups, Highly compatible, the interaction is effectively expressed by physical affinity such as chemical bond with the tackifier or hydrogen bond between mutual functional groups, and the cross-linking agent defined in the present invention. It is possible to obtain a pressure-sensitive adhesive film for surface protection, which is excellent in the characteristics of the present invention, because a chemical bond or a physical affinity is generated between and.

The modified block copolymer used in the present invention or its hydrogenated product (1) is particularly preferably a hydroxyl group,
A modified block copolymer having an atomic group having a functional group selected from an epoxy group, an amino group, a silanol group, and an alkoxysilane group bonded thereto or a hydrogenated product thereof.

In the present invention, an atomic group having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is preferably an atomic group represented by the following formulas (1) to (14). An atomic group selected from those represented by the formulas can be given.

[0035]

[Chemical 3] (In the above formula, R ^{1 to} R ⁴ are hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a carbon group having 1 to 24 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. A hydrogen group, R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group, where R ^{1 to} R ⁴ hydrocarbon group, and the hydrocarbon chain of R ^5, hydroxyl, epoxy group, a silanol group, in bonding mode other than alkoxysilane groups, oxygen, nitrogen, may be bonded silicon .R ⁶ is Hydrogen or an alkyl group having 1 to 8 carbon atoms.)

In the present invention, it is used to obtain a modified block copolymer to which an atomic group having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is bonded, or a hydrogenated product thereof. Examples of the modifying agent include the following.

For example, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane,
Diglycidyl aniline, diglycidyl orthotoluidine, γ-glycidoxyethyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ- Glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldisilane Ethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis (γ -Glycidoxypropyl) dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis ( γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycidoxypropyl) methylmethoxysilane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, Bis (γ-glycidoxypropyl Methylbutoxysilane, bis (γ-glycidoxypropyl) methylphenoxysilane, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryl Roxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis (γ-methacryloxypropyl) dimethoxysilane, tris (γ-methacryloxypropyl) methoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tri Methoxysilane, β-
(3,4-Epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl)
Ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyl-
Ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β-
(3,4-Epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β- (3,4
-Epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane,
β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,3
4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl)
Ethyl-dimethylbutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-
Diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3
-Diethyl-2-imidazolidinone, N, N'-dimethylpropyleneurea, N-methylpyrrolidone and the like can be mentioned.

By reacting the above modifying agent, the residue of the modifying agent to which an atomic group having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is bonded, is bonded. A modified block copolymer having the above structure is obtained. When a functional group-containing modifier is added to the living end of the block copolymer, the living end of the block copolymer may be a polymer block A mainly composed of vinyl aromatic hydrocarbon or a polymer block mainly composed of conjugated diene. Any of B may be used, but in order to obtain a pressure-sensitive adhesive layer having excellent holding power, it is preferable that the polymer block A is bonded to the end.

In the present invention, the amount of the functional group-containing modifier used for the addition reaction on the living end of the block copolymer is 1 equivalent of the living end of the block copolymer.
It is recommended to use more than 0.5 equivalents and 10 equivalents or less, preferably more than 0.7 equivalents and 5 equivalents or less, more preferably more than 0.9 equivalents and 4 equivalents or less. In the present invention, the amount of the living terminal of the block copolymer may be calculated from the amount of the organolithium compound used for the polymerization and the number of lithium atoms bound to the organolithium compound, or obtained. It may be calculated from the number average molecular weight of the block copolymer.

In the present invention, when the hydrogenated product of the modified block copolymer is used as the component (1), it is possible to suppress gelation in the processing of the pressure-sensitive adhesive layer used for the surface protective film and deterioration due to long-term storage. The hydrogenated product of the modified block copolymer can be obtained by hydrogenating the modified block copolymer obtained above. The hydrogenation catalyst is not particularly limited and is conventionally known (a) Ni, Pt, P.
A supported heterogeneous hydrogenation catalyst in which a metal such as d or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like, (b)
A so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe and Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (c) T
A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as i, Ru, Rh and Zr is used. Specific hydrogenation catalysts include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-3970, and Japanese Patent Publication No. 1-5385.
The hydrogenation catalysts described in Japanese Patent Publication No. 1 and Japanese Patent Publication No. 2-9041 can be used. Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound.

As the titanocene compound, Japanese Patent Laid-Open No. 8-1
The compounds described in Japanese Patent Publication No. 09219 can be used,
Specific examples include compounds having a ligand having a (substituted) cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. . Examples of the reducing organic metal compound include organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds and organic zinc compounds.

The hydrogenation reaction is preferably carried out in the temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to
15 MPa, more preferably 0.2 to 10 MPa, further preferably 0.3 to 5 MPa is recommended. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction is a batch process,
Either a continuous process or a combination thereof can be used.

In the hydrogenated product of the modified block copolymer used in the present invention, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound can be arbitrarily selected according to the purpose and is not particularly limited. 70% or more, preferably 80% or more, more preferably 90% or more of the unsaturated double bond based on the conjugated diene compound in the block copolymer may be hydrogenated, or only a part thereof may be hydrogenated. It may be. When hydrogenating only a part, it is preferable that the hydrogenation rate is 10% or more and less than 70%, or 15% or more and less than 65%, and if desired, 20% or more and less than 60%.

Further, in the present invention, in the hydrogenated modified block copolymer, the hydrogenation rate of vinyl bond based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more is recommended in order to obtain a pressure-sensitive adhesive layer having excellent thermal stability.
Here, the hydrogenation rate of vinyl bonds means the ratio of hydrogenated vinyl bonds to the vinyl bonds based on the conjugated diene before hydrogenation incorporated in the block copolymer.

The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the modified block copolymer is not particularly limited, but is preferably 50% or less, more preferably 30% or less, 20% or less is recommended. The hydrogenation rate can be known by a nuclear magnetic resonance apparatus (NMR).

The modified block copolymer or hydrogenated product thereof used in the present invention has a weight average molecular weight of 30,000 or more from the viewpoint of holding power of the pressure-sensitive adhesive layer, melt viscosity, processability, and phase with the tackifier. From the viewpoint of compatibility, it is preferably 1,000,000 or less,
More preferably 40,000 to 500,000, and even more preferably 50,000 to 3
It is 0,000.

In the present invention, the amount of vinyl bond based on the conjugated diene compound in the modified block copolymer can be known by using a nuclear magnetic resonance apparatus (NMR). The hydrogenation rate can also be known using the same device. The weight average molecular weight of the modified block copolymer or the hydrogenated product thereof is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is determined by measuring the standard curve of commercially available polystyrene. (Prepared using the peak molecular weight of standard polystyrene).

The solution of the modified block copolymer or hydrogenated product thereof obtained as described above is removed of the catalyst residue, if necessary, and the modified block copolymer or hydrogenated product thereof is separated from the solution. be able to. As a method for separating the solvent, for example, a method in which a polar solvent that is a poor solvent for the polymer such as acetone or alcohol is added to a solution after polymerization or hydrogenation to precipitate and recover the polymer, a modified block copolymer Alternatively, a method of adding the solution of the hydrogenated product to hot water with stirring and removing the solvent by steam stripping to recover, or a method of directly heating the polymer solution and distilling the solvent can be mentioned. . The modified block copolymer used in the present invention or a hydrogenated product thereof may contain stabilizers such as various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers and amine-based stabilizers. .

In the present invention, as the modified block copolymer of the component (1) or its hydrogenated product, one obtained by using (1-A) an organolithium compound as a polymerization catalyst and containing vinyl aromatic hydrocarbon as a main component A modified block copolymer obtained by adding a functional group-containing modifier to the living end of a block copolymer consisting of the polymer block A of 1 and one polymer block B mainly composed of a conjugated diene, or its hydrogenation Things 20 ~
90 wt%, preferably 25-80 wt%, (1-B)
A block copolymer comprising at least two polymer blocks A containing vinyl aromatic hydrocarbon as a main component and at least one polymer block B mainly containing a conjugated diene, obtained by using an organolithium compound as a polymerization catalyst. A modified block copolymer obtained by addition reaction of a functional group-containing modifying agent at the living end or a hydrogenated product thereof at 80 to 10 wt%, preferably 75 to 20 wt%, is used. It is recommended to do so in order to obtain a pressure-sensitive adhesive layer having an excellent balance of holding power, tackiness and melt viscosity.

The molecular weight of these modified block copolymers or hydrogenated products thereof (the molecular weight in terms of standard polystyrene measured by GPC) is 30,000 to 1 for component (1-A).
50,000, preferably 40,000 to 140,000, more preferably 50,000 to
It is 130,000, and the component (1-B) is 100,000 to 300,000, preferably 120,000 to 280,000, and more preferably 140,000 to 260,000. It is particularly preferable in terms of points. The average molecular weights of the component (1-A) and the component (1-B) need to be set to the molecular weights in the range described in the weight molecular weight of the modified block copolymer used in the present invention or the hydrogenated product thereof. is there.

There is no particular limitation on the kind of the tackifier as the component (2) used in the present invention, and the rosin-based terpene-based resin, hydrogenated rosin-based terpene-based resin, coumarone-based resin and phenol-based resin are used. , Terpene-phenolic resins, aromatic hydrocarbon resins, and known tackifiers such as aliphatic hydrocarbon resins. These tackifiers may be used alone or in combination of two or more. May be used. As specific examples of the tackifier, those described in "Rubber / Plastic Blended Chemicals" (edited by Rubber Digest) can be used. The tackifier is used in an amount of 3 to 200 parts by mass, preferably 5 to 150 parts by mass, relative to 100 parts by mass of the component (1). When the amount used exceeds 200 parts by mass, the adhesive strength after long-term sticking is strong and adhesive residue is apt to occur during peeling, which is not preferable. On the other hand, if it is less than 3 parts by mass, sufficient adhesive force cannot be obtained, which is not preferable.

In the pressure-sensitive adhesive layer composition of the present invention, known naphthene-based and paraffin-based process oils and mixed oils thereof can be used as a softening agent.
By adding the softening agent, the viscosity of the pressure-sensitive adhesive layer composition is lowered, so that the processability is improved and the tackiness is improved. The blending amount of these softening agents is 0 to 200 parts by mass, preferably 0 to 100 parts by mass, relative to 100 parts by mass of the component (1), from the viewpoint of color tone, holding power, and thermal stability of the pressure-sensitive adhesive layer. Ranges are preferred.

In the present invention, a crosslinking agent having reactivity with the functional group moiety of component (1) can be used as component (3). The cross-linking agent of the component (3) is a cross-linking agent having a functional group reactive with the functional group of the modified block copolymer or its hydrogenated product (1), preferably a carboxyl group, an acid anhydride group, an isocyanate. It is a cross-linking agent having a functional group selected from a group, an epoxy group, a silanol group, and an alkoxysilane group. When using a cross-linking agent, the compounding amount is
0.01 to 20 parts by mass, preferably 0.03 to 10 parts by mass, relative to 100 parts by mass of the modified block copolymer of the component (1).
Parts by mass, more preferably 0.05 to 7 parts by mass. When the cross-linking agent is used in such a blending amount, it is possible to obtain a surface-protective pressure-sensitive adhesive film which is excellent in anchoring force and adhesive force and does not cause adhesive residue after sticking.

Specific examples of the cross-linking agent of the component (3) include, as the cross-linking agent having a carboxyl group, maleic acid, fumaric acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid. Carboxylic acid, cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid and other aliphatic carboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, pyromellitic acid and other aromatic compounds Examples thereof include carboxylic acid.

As the crosslinking agent having an acid anhydride group, maleic anhydride, itaconic anhydride, pyromellitic dianhydride, cis-4-cyclohexane-1,2-dicarboxylic acid anhydride, 1,2,4,5- Benzenetetracarboxylic dianhydride, 5- (2,5-dioxytetrahydroxyfuryl)
Examples thereof include -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride.

Examples of the crosslinking agent having an isocyanate group include toluylene diisocyanate, diphenylmethane diisocyanate and polyfunctional aromatic isocyanate.

As the crosslinking agent having an epoxy group, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene glycol diglycidyl, terephthalic acid diglycidyl ester. Acrylate etc. are mentioned.

Examples of the crosslinking agent having a silanol group include a hydrolyzate of an alkoxysilane compound described as a modifier used for obtaining the block copolymer of the component (1).

Examples of the crosslinking agent having an alkoxysilane group include bis- (3-triethoxysilylpropyl) -tetrasulfane, bis- (3-triethoxysilylpropyl) -disulfane and ethoxysiloxane oligomer.

In the present invention, a particularly preferable crosslinking agent has a carboxylic acid having two or more carboxyl groups or an acid anhydride thereof, or two or more acid anhydride groups, isocyanate groups, epoxy groups, silanol groups and alkoxysilane groups. Cross-linking agent, for example, maleic anhydride, pyromellitic dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluylene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane, etc. .

In the present invention, the secondary modified block copolymer obtained by previously reacting the above component (1) with the component (3) (defined as the component (1 ′) in the present invention) is blended with the component (2). Can be used as a pressure-sensitive adhesive layer constituent composition. When the component (1) is reacted with the component (3) in advance, the component (1)
The amount of the component (3) is 0.3 to 10 mol, preferably 0.4 to 5 mol, and more preferably 0.5 to 4 mol, per equivalent of the functional group bonded to. Examples of the method of previously reacting the component (1) with the component (3) include a melt-kneading method described below and a method of dissolving or dispersing and mixing each component in a solvent and the like to react. When the component (1 ′) thus obtained is blended with the component (2) to form a pressure-sensitive adhesive layer-constituting composition, the total amount of the component (1 ′) and the component (2) is 100 parts by mass. Further, 0.001 to 20 parts by mass of the component (3) can be blended.

In the present invention, the method of previously reacting the component (1) with the component (3) is not particularly limited, and
Known methods can be used. For example, a melt kneading method using a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, a multi-screw extruder, etc., after melting or dispersing and mixing each component, heating the solvent A method of removing it is used. In the present invention, the melt-kneading method using an extruder is preferable from the viewpoint of productivity and good kneading property.

Furthermore, if necessary, stabilizers such as antioxidants and light stabilizers may be added to the pressure-sensitive adhesive layer composition of the present invention.

Examples of the antioxidant include 2,6-di-
t-Butyl-4-methylphenol, n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t) -Butylphenol), 2,2 '
-Methylenebis (4-ethyl-6-t-butylphenol), 2,4-bis [(octylthio) methyl] -o-
Cresol, 2-t-butyl-6- (3-t-butyl-
2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6-
[1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2- [1- (2
-Hydroxy-3,5-di-tert-pentylphenyl)] acrylate and other hindered phenolic antioxidants; dilauryl thiodipropionate, lauryl stearyl thiodipropionate pentaerythritol-
Sulfur-based antioxidants such as tetrakis (β-laurylthiopropionate); phosphorus-based antioxidants such as tris (nonylphenyl) phosphite and tris (2,4-di-t-butylphenyl) phosphite Can be mentioned.

As the light stabilizer, for example, 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-t
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3 ', 5'-di-t-butylphenyl)-
Examples thereof include benzotriazole-based UV absorbers such as 5-chlorobenzotriazole, benzophenone-based UV absorbers such as 2-hydroxy-4-methoxybenzophenone, and hindered amine-based light stabilizers.

In addition to the above stabilizers, the pressure-sensitive adhesive layer composition used in the present invention may optionally contain pigments such as red iron oxide and titanium dioxide; waxes such as paraffin wax, microcristan wax, low molecular weight polyethylene wax, and the like; Amorphous polyolefin, polyolefin-based or low molecular weight vinyl aromatic thermoplastic resin such as ethylene-ethyl acrylate copolymer; natural rubber; polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, chloroprene rubber,
Synthetic rubbers such as acrylic rubber, isoprene-isobutylene rubber, polypentenamer rubber, and styrene-isoprene block copolymers other than the present invention may be added. Other examples include those described in "Rubber / Plastic Blended Chemicals" (edited by Rubber Digest).

Examples of the nonpolar resin used as the resin film in the present invention include polystyrene resins and polyolefin resins. Specific examples of polystyrene resins include polystyrene, high-impact polystyrene (HIPS), polymethylstyrene, and styrene-
Examples thereof include a butadiene block copolymer resin. As the polyolefin resin, ethylene, carbon number 3 to 12
Is not particularly limited as long as it is a resin obtained by polymerizing a monomer selected from α-olefins such as propylene, 1-butene, isobutylene, 4-methyl-1-pentene and 1-octene. For example, polyethylene,
Examples thereof include polypropylene, ethylene-propylene copolymer, polybutene, ethylene-butene copolymer, propylene-butene copolymer, ethylene-octene copolymer and the like. The copolymer may be a random copolymer, a block copolymer, or a mixture thereof. Also,
The polyolefin resin is a copolymer rubber of two or more kinds of α-olefins, or an olefinic thermoplastic elastomer such as a copolymer of α-olefins and other monomers.
May be contained. As these copolymer rubbers,
Examples thereof include ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EBR), ethylene-octene copolymer rubber and ethylene-propylene-diene copolymer rubber (EPDM).

The polar resin used as the resin film in the present invention includes polyester resins such as polyethylene terephthalate and polybutylene terephthalate, nylon 11, nylon 12, nylon 6, nylon 6,1.
0, nylon 6,12, nylon 6,6, nylon 4,
Polyamide resin, polycarbonate resin, polyurethane resin such as 6 and the like, polymer having an imide bond in the main chain, for example, polyimide, polyamino bismaleimide (poly bismaleimide), bismaleimide / triazine resin, polyamide imide, polyether imide, etc. Polyimide resin, polymer of formaldehyde or trioxane, polyoxymethylene resin such as copolymer of formaldehyde or trioxane with other aldehyde, cyclic ether, epoxide, isocyanate, vinyl compound, polyether sulfone or polyallyl sulfone Polysulfone resin such as polyphenylene ether resin such as poly (2,6-dimethyl-1,4-phenylene) ether, polyphenylene sulfide, polyphenylene sulfide such as poly 4,4′-diphenylene sulfide Nylene sulfide resin, polyarylate resin which is a polycondensation polymer composed of bisphenol A and phthalic acid component, polyketone resin, vinyl aromatic compound and other vinyl monomers such as vinyl acetate, acrylic acid and methyl acrylate. Acrylic esters, methacrylic acid and methyl methacrylate, ethyl methacrylate, methacrylic acid esters such as butyl methacrylate, acrylonitrile, copolymer resins with methacrylonitrile, acrylonitrile-butadiene-styrene copolymer resin (ABS), Methacrylic acid ester-butadiene-styrene copolymer resin (MBS), a copolymer of ethylene containing 50 wt% or more of ethylene and another monomer copolymerizable therewith, for example, an ethylene-vinyl acetate copolymer and the same. Hydrolyzate, ethi -Polyethylene resin copolymerized with polar monomers such as acrylic acid ionomer, a copolymer of propylene containing 50 wt% or more of propylene and another monomer copolymerizable therewith, for example, propylene-ethyl acrylate copolymer A polypropylene resin copolymerized with a polar monomer such as a polymer, a polyvinyl acetate resin which is a copolymer of vinyl acetate having a vinyl acetate content of 50 wt% or more, and another monomer copolymerizable therewith, Hydrolysates thereof, polymers of acrylic acid and its esters and amides, polymers of methacrylic acid and its esters and amides, acrylic acid or methacrylic acid containing 50% by weight or more of these acrylic acid or methacrylic acid-based monomers. Polyacrylate, which is a copolymer of a base monomer and another monomer that can be copolymerized with it Resin, acrylonitrile and / or methacrylonitrile polymer, a nitrile resin which is a copolymer of an acrylonitrile monomer containing 50% by weight or more of these acrylonitrile monomers and a monomer copolymerizable therewith , Paraoxybenzoic acid, terephthalic acid, isophthalic acid, 4,4′-dihydroxydiphenyl or derivatives thereof, and polyoxybenzoyl polymers such as polymers or copolymers produced by polycondensation. Specific examples of suitable polar resins in the present invention include polyester resins, polyamide resins, polycarbonate resins, and polyurethane resins.

The resin film in the present invention is preferably made of a material which can be melt-extruded to be a support for the pressure-sensitive adhesive film for surface protection among these nonpolar resins or polar resins. Examples of such materials From the viewpoint of performance and price, polyethylene, homo or block polypropylene, polyethylene terephthalate,
Polyester resin such as polybutylene terephthalate,
Those comprising a polyamide resin, an ethylene-vinyl acetate copolymer and a hydrolyzate thereof are preferred.

The thickness of each layer in the pressure-sensitive adhesive film for surface protection of the present invention is preferably as follows. That is,
The pressure-sensitive adhesive layer preferably has a thickness of 300 μm or less, more preferably 5 to 100 μm. The resin film layer having a thickness of 5 mm or less, preferably 3 mm or less, more preferably 1 mm or less is preferably used. Particularly preferably 300 μm
The following is more preferably 10 to 200 μm. In addition,
Generally, a sheet having a thickness of more than 300 μm is called a sheet, but in the present invention, the sheet including them is called a film.

The pressure-sensitive adhesive film for surface protection of the present invention is produced, for example, as follows. That is, the pressure-sensitive adhesive component and the thermoplastic resin component, in the melt co-extruder, in two flows, that is, the adhesive layer forming fluid and the support film forming fluid to join in the die mouth. It is manufactured by forming and extruding a single fluid, and combining the pressure-sensitive adhesive layer and the resin film layer. Of course, it can be easily produced by applying the pressure-sensitive adhesive layer composition to the resin film.

Since the surface-protective adhesive film obtained by the method of the present invention has excellent anchoring force, the surface-protective adhesive film may be temporarily attached to a metal plate or the like for sheet metal processing or left for a long period of time. Also has the feature that no adhesive residue occurs. Further, even if the product is pasted and stored for a long period of time, the pressure-sensitive adhesive layer is hardly deteriorated and no adhesive residue is observed at all, which is a remarkable effect.

[0073]

EXAMPLES The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. The measurement of the performance of the block copolymer, the measurement of the physical properties of the pressure-sensitive adhesive film for surface protection, the preparation of the hydrogenation catalyst, and the preparation of the block copolymer were carried out by the following methods.

1. Measurement of the performance of the block copolymer (1) Styrene content Using an ultraviolet spectrophotometer (Hitachi UV200), 262
It was calculated from the absorption intensity at nm.

(2) Vinyl bond amount and hydrogenation rate Nuclear magnetic resonance apparatus (BRUXER, DPX-400)
Was measured using.

(3) Molecular weight GPC (apparatus: LC10 manufactured by Shimadzu Corporation, column: Shimpac GPC805 + GPC80 manufactured by Shimadzu Corporation)
4 + GPC804 + GPC803). Tetrahydrofuran is used as the solvent, and the measurement condition is a temperature of 35 ° C.
I went there. The molecular weight is a weight average molecular weight obtained by using a calibration curve (prepared by using the peak molecular weight of standard polystyrene) obtained by measuring the standard polystyrene of the chromatogram.

(4) Ratio of unmodified block copolymer A sample containing a modified block copolymer and a low molecular weight internal standard polystyrene by applying the property that the modified component is adsorbed to a GPC column using silica gel as a packing material. For the solution,
The ratio of the modified block copolymer to the standard polystyrene in the chromatogram measured in the above (3), and the modified block copolymer weight to the standard polystyrene in the chromatogram measured by the silica-based column GPC [device is DuPont: Zorbax]. The ratios of coalescence were compared, and the amount adsorbed on the silica column was measured from the difference between them. The ratio of the unmodified block copolymer is the ratio of those that were not adsorbed on the silica column.

2. Measurement of Physical Properties of Pressure-Sensitive Adhesive Film for Surface Protection The physical properties of the pressure-sensitive adhesive film for surface protection were measured by taking out the pressure-sensitive adhesive composition obtained by the following method in a molten state and measuring a thickness of 100
An adhesive film was prepared by coating a resin film having a thickness of 15 μm to a thickness of 15 μm, and the anchoring force, the adhesive force, and the adhesive residue after attachment were measured by the following methods.

(1) Anchoring force (g / 20 mm) After the film was pressure-bonded between the adhesive surfaces, the film was stored at 70 ° C. for 1 hour, and a 180 ° peeling test was performed at 20 ° C. × 65% relative humidity. (2) Adhesive strength (g / 25 mm) A film was attached to a SUS304 stainless steel plate, and 18
A 0 degree peeling test was performed. (3) Adhesive residue after attachment A film is attached to a SUS304 stainless steel plate,
After standing for 6 months at 0 ° C, the presence or absence of adhesive residue was observed at 20 ° C x 65% relative humidity.

3. Preparation of hydrogenation catalyst In the preparation of the block copolymer below, the hydrogenation catalyst used for the hydrogenation reaction was prepared by the following method. 1) Hydrogenation catalyst I 1 liter of dried and purified cyclohexane was charged into a reaction vessel purged with nitrogen, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added, and 200 mmol of trimethylaluminum was added with sufficient stirring. An n-hexane solution was added and reacted at room temperature for about 3 days.

2) Hydrogenation catalyst II 2 liters of dried and purified cyclohexane was charged into a reaction vessel purged with nitrogen, and 40 mmol of bis (η5-cyclopentadienyl) titanium di- (p-tolyl) and a molecular weight of about 1, were added. Of 1,2-polybutadiene (1,2-
After dissolving 150 grams of vinyl bond (about 85%), n
A cyclohexane solution containing 60 mmol of -butyllithium was added, and the mixture was reacted at room temperature for 5 minutes. Immediately, 40 mmol of n-butanol was added and stirred, and the mixture was stored at room temperature.

4. Preparation of Block Copolymer 1) Block Copolymer 1 An autoclave equipped with a stirrer and a jacket was washed, dried and purged with nitrogen, and a cyclohexane solution (concentration 20 wt%) containing 10 parts by mass of styrene purified in advance was added.
Then, n-butyllithium and tetramethylethylenediamine are added, and after polymerization at 70 ° C for 30 minutes, a cyclohexane solution (concentration 20 wt%) containing 81 parts by mass of previously purified 1,3-butadiene is added and the mixture is heated at 70 ° C for 1 hour. Polymerization was performed, and a cyclohexane solution containing 9 parts by mass of styrene was added, and the mixture was polymerized at 70 ° C. for 30 minutes. Then, 1,3-dimethyl-2-imidazolidinone (hereinafter,
The modifier M1) was reacted equimolarly with the n-butyllithium used for the polymerization. The block copolymer obtained is
The styrene content was 19 wt% and the vinyl bond content in the polybutadiene part was 36%. To the block copolymer obtained above, 100 ppm of the hydrogenation catalyst I as Ti was added, and the hydrogenation reaction was carried out for 1 hour at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Methanol was then added, and then octadecyl-3- (3,5-di-t-butyl-4- as a stabilizer.
Hydroxyphenyl) propionate was added in an amount of 0.3 part by mass based on 100 parts by mass of the block copolymer. The properties of the obtained block copolymer (hereinafter referred to as block copolymer 1) are shown in Table 1. The ratio of the unmodified block copolymer mixed in the block copolymer 1 was 20 wt%.

2) Block Copolymer 2 Block Copolymer 2 was prepared in the same manner as Block Copolymer 1 except that no modifier was added. The block copolymer 2 had a styrene content of 19 wt% and a vinyl bond content of 36% in the polybutadiene portion before the hydrogenation reaction. The properties of the resulting block copolymer 2 are shown in Table 1.

3) Block Copolymer 3 Block Copolymer 1 except that the hydrogenation rate was 60%.
A block copolymer 3 was produced in the same manner as in. The block copolymer 3 had a styrene content of 19% by weight and a vinyl bond content of 36% in the polybutadiene portion before the hydrogenation reaction. The properties of the obtained block copolymer 3 are shown in Table 1. The ratio of the unmodified block copolymer mixed in the block copolymer 3 was 25 wt%.

4) Block Copolymer 4 An autoclave equipped with a stirrer and a jacket was washed, dried and purged with nitrogen, and a cyclohexane solution (concentration 20 wt%) containing 5 parts by mass of 1,3-butadiene purified in advance was added. Next, after adding n-butyllithium and tetramethylethylenediamine and polymerizing at 70 ° C. for 15 minutes,
A cyclohexane solution containing 15 parts by mass of styrene purified in advance (concentration: 20 wt%) was added, and polymerization was performed at 70 ° C. for 30 minutes. Then, a cyclohexane solution containing 66 parts by mass of 1,3-butadiene was added and polymerized at 70 ° C. for 30 minutes, and a cyclohexane solution containing 14 parts by mass of styrene was added and polymerized at 70 ° C. for 30 minutes. Then, tetraglycidyl-1,3-bisaminomethylcyclohexane (hereinafter, modifier M2) as a modifier was reacted in a molar amount of 0.25 times with respect to n-butyllithium used for the polymerization. The obtained block copolymer had a styrene content of 29 wt% and a polybutadiene portion vinyl bond content of 42%. The hydrogenated catalyst II was added to the block copolymer obtained above with Ti.
As a hydrogenation reaction was carried out for 1 hour at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Methanol was then added, and then octadecyl-3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate was added to 0.3 per 100 parts by weight of the block copolymer.
Added by mass. The properties of the obtained block copolymer (hereinafter referred to as block copolymer 4) are shown in Table 1. The ratio of the unmodified block copolymer mixed in the block copolymer 4 was 25 wt%.

5) Block Copolymer 5 Block Copolymer 5 was prepared in the same manner as Block Copolymer 4 except that hydrogenation was not carried out. Block copolymer 5
Had a styrene content of 29% by weight and a vinyl bond content of 42% in the polybutadiene portion. The properties of the obtained block copolymer 5 are shown in Table 1. In addition, the block copolymer 5
The ratio of the unmodified block copolymer mixed in is 20w
It was t%.

6) Block Copolymer 6 An autoclave equipped with a stirrer and a jacket was washed, dried and purged with nitrogen, and a cyclohexane solution (concentration 20 wt%) containing 22 parts by mass of styrene purified in advance was added.
Next, n-butyllithium and tetramethylethylenediamine are added, and after polymerization at 70 ° C. for 1 hour, a cyclohexane solution (concentration 20 wt%) containing 60 parts by mass of pre-purified 1,3-butadiene is added and the mixture is heated at 70 ° C. for 1 hour. After polymerization, a cyclohexane solution containing 18 parts by mass of styrene was added, and polymerization was carried out at 70 ° C. for 1 hour. Then, γ-glycidoxypropyltrimethoxysilane (hereinafter, modifier M3) was used as a modifier in equimolar reaction with n-butyllithium used for the polymerization. The obtained block copolymer had a styrene content of 40 wt% and a vinyl bond content of 28% in the polybutadiene portion. The hydrogenated catalyst I as Ti was added to the block copolymer obtained above in an amount of 100 ppm.
After the addition, hydrogenation reaction was carried out for 1 hour at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Methanol is then added, and then octadecyl-3- (3,5-di-t-butyl-
0.3 parts by mass of 4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. The properties of the obtained block copolymer (hereinafter referred to as block copolymer 6) are shown in Table 1. The ratio of the unmodified block copolymer mixed in the block copolymer 6 was 25 wt%.

7) Block Copolymer 7 n- using SiCl ₄ as a coupling agent in the polymerization
A block copolymer 7 having no functional group was obtained in the same manner as in the block copolymer 6 except that the reaction was performed in 1/4 mol with respect to butyllithium. The block copolymer 7 had a styrene content of 40 wt% and a vinyl bond content of 28% in the polybutadiene portion before the hydrogenation reaction. The properties of the resulting block copolymer 7 are shown in Table 1.

[0089]

[Table 1]

Example 1 100% of block copolymer 1 was prepared.
CLEARON P105 as a tackifier with respect to parts by mass
(Yasuhara Chemical; hereinafter N1) 40 parts by mass, maleic anhydride as a cross-linking agent (hereinafter, cross-linking agent D1) 0.5
Parts by mass, and 2-t-amyl-6- [1- as the stabilizer
(3,5-di-t-amyl-2-hydroxyphenyl)
Ethyl] -4-t-aminophenyl acrylate was added to 0.
3 parts by mass were blended and melt-kneaded in a container equipped with a stirrer at 180 ° C. for 2 hours to obtain a pressure-sensitive adhesive composition. An adhesive film was produced using the obtained adhesive composition and a polyethylene film, and physical properties were measured. Table 2 shows the physical properties of the obtained adhesive film.

[Example 2] An adhesive composition was obtained in the same manner as in Example 1 except that the crosslinking agent was not added. An adhesive film was produced using the obtained adhesive composition and a polyethylene film, and physical properties were measured. The physical properties of the obtained adhesive film are shown in Table 2.

[Comparative Example 1] An adhesive film was obtained in the same manner as in Example 1 except that the block copolymer 2 was used. Table 2 shows the physical properties of the obtained adhesive film.

[Example 3] 100 of block copolymer 3 was used.
Alcon M100 as a tackifier for parts by mass
(Arakawa Chemical Co .; N2 below) 30 parts by mass, tetraglycidyl-1,3-bisaminomethylcyclohexane (hereinafter, cross-linking agent D2) 0.5 part by mass as a cross-linking agent, and 2-t-amyl as a stabilizer. -6- [1- (3,5-di-t
-Amyl-2-hydroxyphenyl) ethyl] -4-t
-Containing 0.3 parts by mass of aminophenyl acrylate,
Melt-kneading was performed at 180 ° C. for 2 hours in a container equipped with a stirrer to obtain a pressure-sensitive adhesive composition. An adhesive film was produced using the obtained adhesive composition and a polyethylene film, and physical properties were measured. Table 2 shows the physical properties of the obtained adhesive film.

[Example 4] 100 of block copolymer 4 was used.
40 parts by mass of N1 as a tackifier with respect to parts by mass,
1.0 part by mass of D1 as a cross-linking agent and 2 as a stabilizer
-T-amyl-6- [1- (3,5-di-t-amyl-
0.3 parts by mass of 2-hydroxyphenyl) ethyl] -4-t-aminophenyl acrylate was blended and melt-kneaded in a container with a stirrer at 180 ° C. for 2 hours to obtain a pressure-sensitive adhesive composition. An adhesive film was produced using the obtained adhesive composition and a polyethylene film, and physical properties were measured. Table 2 shows the physical properties of the obtained adhesive film.

[Example 5] Block copolymer 5 was added to 100
55 parts by mass of N2 as a tackifier with respect to parts by mass,
5.0 parts by mass of D2 as a cross-linking agent and 2 as a stabilizer
-T-amyl-6- [1- (3,5-di-t-amyl-
0.3 parts by mass of 2-hydroxyphenyl) ethyl] -4-t-aminophenyl acrylate was blended and melt-kneaded in a container with a stirrer at 180 ° C. for 2 hours to obtain an adhesive composition. An adhesive film was produced using the obtained adhesive composition and a polyethylene film, and physical properties were measured. Table 2 shows the physical properties of the obtained adhesive film.

Example 6 100% of block copolymer 6 was used.
80 parts by mass of N1 as a tackifier with respect to parts by mass,
0.5 part by mass of D1 as a crosslinking agent and 2 as a stabilizer
-T-amyl-6- [1- (3,5-di-t-amyl-
0.3 parts by mass of 2-hydroxyphenyl) ethyl] -4-t-aminophenyl acrylate was blended and melt-kneaded in a container with a stirrer at 180 ° C. for 2 hours to obtain a pressure-sensitive adhesive composition. An adhesive film was produced using the obtained adhesive composition and a polyethylene film, and physical properties were measured. Table 2 shows the physical properties of the obtained adhesive film.

[Comparative Example 2] An adhesive film was obtained in the same manner as in Example 6 except that the block copolymer 7 was used. Table 2 shows the physical properties of the obtained adhesive film.

[0098]

[Table 2]

Example 7 An adhesive film was prepared in the same manner as in Example 1 except that a polyethylene terephthalate (PET) film was used as the support film, and its physical properties were measured. Table 3 shows the physical properties of the obtained adhesive film.

[Example 8] An adhesive film was prepared in the same manner as in Example 2 except that a polyethylene terephthalate (PET) film was used as the support film, and its physical properties were measured. Table 3 shows the physical properties of the obtained adhesive film.

[Comparative Example 3] An adhesive film was obtained in the same manner as in Example 7 except that the block copolymer 2 was used. Table 3 shows the physical properties of the obtained adhesive film.

Example 9 An adhesive film was prepared in the same manner as in Example 3 except that a polyethylene terephthalate (PET) film was used as the support film, and its physical properties were measured. Table 3 shows the physical properties of the obtained adhesive film.

[Example 10] An adhesive film was prepared in the same manner as in Example 4 except that a polyethylene terephthalate (PET) film was used as the support film, and its physical properties were measured. Table 3 shows the physical properties of the obtained adhesive film.

[Example 11] An adhesive film was prepared in the same manner as in Example 5 except that a polyethylene terephthalate (PET) film was used as the support film, and its physical properties were measured. Table 3 shows the physical properties of the obtained adhesive film.

[Example 12] An adhesive film was prepared in the same manner as in Example 6 except that a polyethylene terephthalate (PET) film was used as the support film, and its physical properties were measured. Table 3 shows the physical properties of the obtained adhesive film.

[Comparative Example 4] An adhesive film was obtained in the same manner as in Example 12 except that the block copolymer 7 was used. Table 3 shows the physical properties of the obtained adhesive film.

[0107]

[Table 3]

Example 13 In the block copolymer 1, 2.1 equivalent per equivalent of the functional group bonded to the block copolymer was obtained.
A mole of the cross-linking agent D1 was blended and melt-kneaded with a 30 mmφ twin-screw extruder at 230 ° C. and a screw rotation speed of 100 rpm to obtain a secondary modified block copolymer of the block copolymer 1 (secondary modified block copolymer a ) Got. Table 4 shows the composition of the secondary modified block copolymer a.

With respect to 100 parts by mass of the second modified block copolymer a, 40 parts by mass of N1 as a tackifier and 2-t-amyl-6- [1- (3,5-di-
t-amyl-2-hydroxyphenyl) ethyl] -4-
0.3 parts by mass of t-aminophenyl acrylate was blended and melt-kneaded in a vessel equipped with a stirrer at 180 ° C. for 2 hours to obtain a pressure-sensitive adhesive composition. An adhesive film was produced using the obtained adhesive composition and a polyethylene film, and physical properties were measured. The physical properties of the obtained adhesive film are shown in Table 5.

[Comparative Example 5] The block copolymer 2 was mixed with 2.1 times mol of the cross-linking agent D1 with respect to the block copolymer, and the mixture was heated at 230 ° C in a 30 mmφ twin-screw extruder at a screw rotation speed of 100 rpm. And melt-kneaded to obtain a cross-linking agent-containing block copolymer (cross-linking agent-containing block copolymer d). The composition of the cross-linking agent-containing block copolymer d is shown in Table 4. An adhesive film was obtained in the same manner as in Example 7 using the cross-linking agent-containing block copolymer d. The physical properties of the obtained adhesive film are shown in Table 5.

Example 14 In the block copolymer 4, 0.9 per equivalent of the functional group bonded to the block copolymer was used.
A mole of the cross-linking agent D2 was blended and melt-kneaded with a 30 mmφ biaxial extruder at 230 ° C. and a screw rotation speed of 100 rpm to obtain a secondary modified block copolymer of the block copolymer D (secondary modified block copolymer b ) Got. Table 4 shows the composition of the secondary modified block copolymer b. With respect to 100 parts by mass of the second modified block copolymer b, 40 parts by mass of N1 as a tackifier and 2-t-amyl- as a stabilizer.
0.3 part by mass of 6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] -4-t-aminophenyl acrylate was added, and the mixture was stirred at 180 ° C. in a container equipped with a stirrer.
× Melt kneading for 2 hours to obtain an adhesive composition. An adhesive film was produced using the obtained adhesive composition and a polyethylene film, and physical properties were measured. The physical properties of the obtained adhesive film are shown in Table 5.

[Example 15] 50 blocks of the block copolymer 1 was prepared.
30 parts by weight, 30 parts by mass of the block copolymer 4, 50 parts by mass of the block copolymer 4, and 3.5 mol of the cross-linking agent D2 per equivalent of the total amount of the functional groups bonded to the block copolymer 1 and the block copolymer 4. The mixture was melt-kneaded with a twin-screw extruder at 230 ° C. and a screw rotation speed of 100 rpm to obtain a secondary modified block copolymer (secondary modified block copolymer c). Table 4 shows the composition of the secondary modified block copolymer c. 40 parts by mass of N1 as a tackifier and 2-t-amyl-6- [1- (3,5-di-t-amyl-) as a stabilizer with respect to 100 parts by mass of the second modified block copolymer c. 2-Hydroxyphenyl) ethyl] -4-t-aminophenyl acrylate was mixed in an amount of 0.3 part by mass, and the content was 180 in a container with a stirrer.
The mixture was melt-kneaded at ℃ × 2 hours to obtain an adhesive composition. An adhesive film was produced using the obtained adhesive composition and a polyethylene film, and physical properties were measured. The physical properties of the obtained adhesive film are shown in Table 5.

[Example 16] An adhesive film was prepared in the same manner as in Example 13 except that a polypropylene film was used as the resin film, and the physical properties were measured. The physical properties of the obtained adhesive film are shown in Table 5.

[0114]

[Table 4]

[0115]

[Table 5]

[Example 17] An adhesive film was prepared in the same manner as in Example 13 except that a polyethylene terephthalate (PET) film was used as the support film, and its physical properties were measured. Table 6 shows the physical properties of the obtained adhesive film.

[Comparative Example 6] An adhesive film was obtained in the same manner as in Example 17, except that the block copolymer d containing a crosslinking agent was used. Table 6 shows the physical properties of the obtained adhesive film.

[Example 18] An adhesive film was prepared in the same manner as in Example 14 except that a polyethylene terephthalate (PET) film was used as the support film, and its physical properties were measured. Table 6 shows the physical properties of the obtained adhesive film.

[Example 19] An adhesive film was prepared in the same manner as in Example 15 except that a polyethylene terephthalate (PET) film was used as the support film, and its physical properties were measured. Table 6 shows the physical properties of the obtained adhesive film.

[0120]

[Table 6]

From the results of Examples 1 to 19 and Comparative Examples 1 to 6, it can be seen that the pressure-sensitive adhesive film for surface protection of the present invention has excellent anchoring force and adhesive force and does not cause adhesive residue even after long-term storage. .

[0122]

The adhesive film for surface protection of the present invention is excellent in anchoring force and adhesive strength, and it is possible to temporarily attach the adhesive film for surface protection to a metal plate or the like for sheet metal processing or leave it for a long time. However, it has the feature that no adhesive residue occurs. Further, it has excellent properties as a surface-protective pressure-sensitive adhesive film even after being stuck and stored for a long period of time.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takaaki Matsuda             1-3-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa               Asahi Kasei Corporation F-term (reference) 4J004 AA05 AB01 CA04 CA06 CB03                       CC02 FA04                 4J040 BA172 BA202 CA081 DB051                       DK012 DM011 EB032 EC002                       EF262 GA05 GA11 GA13                       GA29 HB22 HD32 HD33 JA09                       JB09 KA03 MA02 MA05 MA10                       PA23

Claims (9)

[Claims] (1) At the living end of a block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated dienes. 100 parts by mass of a modified block copolymer obtained by addition reaction of a functional group-containing modifier or a hydrogenated product thereof, and (2) a tackifier of 3 to 200 parts by mass,
A pressure-sensitive adhesive film for surface protection, comprising a resin film and a pressure-sensitive adhesive layer containing 2. (1) At the living end of a block copolymer comprising at least one polymer block A mainly containing vinyl aromatic hydrocarbons and at least one polymer block B mainly containing conjugated dienes. 100 parts by mass of a modified block copolymer obtained by addition reaction of a functional group-containing modifier or a hydrogenated product thereof, and (2) a tackifier of 3 to 200 parts by mass,
(3) A pressure-sensitive adhesive film for surface protection, comprising a resin film, and a pressure-sensitive adhesive layer containing 0.01 to 20 parts by mass of a cross-linking agent having reactivity with the functional group portion of component (1). 3. A living terminal of a block copolymer comprising (1 ′) at least one polymer block A mainly containing vinyl aromatic hydrocarbons and at least one polymer block B mainly containing conjugated dienes. A modified block copolymer obtained by addition-reacting a functional group-containing modifying agent or a hydrogenated product (1) thereof with a cross-linking agent reactive with the functional group bonded to the component (1) is added to the functional group. 0.3 to 1 per equivalent
A pressure-sensitive adhesive film for surface protection, which is obtained by forming a pressure-sensitive adhesive layer containing 100 parts by mass of a second modified block copolymer reacted with 0 mol and (2) 3 to 200 parts by mass of a tackifier on a resin film. . 4. A modified block in which the modified block copolymer or its hydrogenated product (1) is bonded to an atomic group having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. The pressure-sensitive adhesive film for surface protection according to claim 1, which is a copolymer or a hydrogenated product thereof. 5. The functional group-containing modifier is a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group in the block copolymer by an addition reaction with the living terminal of the block copolymer. The surface protective pressure-sensitive adhesive film according to any one of claims 1 to 4, which is a modified agent having a functional group that forms a modified block copolymer to which an atomic group having is bonded, or a hydrogenated product thereof. 6. The crosslinking agent is a carboxyl group, an acid anhydride group,
The pressure-sensitive adhesive film for surface protection according to claim 2, which is a crosslinking agent having a functional group selected from an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group. 7. A modified block copolymer or a hydrogenated product (1) thereof, wherein at least one atomic group having a functional group selected from the following formulas (1) to (14) is bonded. The pressure-sensitive adhesive film for surface protection according to any one of claims 1 to 6, which is a polymer or a hydrogenated product thereof. [Chemical 1] (In the above formula, R ^{1 to} R ⁴ are hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a carbon group having 1 to 24 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. A hydrogen group, R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group, where R ^{1 to} R ⁴ hydrocarbon group, and the hydrocarbon chain of R ^5, hydroxyl, epoxy group, a silanol group, in bonding mode other than alkoxysilane groups, oxygen, nitrogen, may be bonded silicon .R ⁶ is Hydrogen or an alkyl group having 1 to 8 carbon atoms.) 8. The pressure-sensitive adhesive film for surface protection according to claim 1, wherein the resin film is a resin film made of a non-polar resin. 9. The pressure-sensitive adhesive film for surface protection according to claim 1, wherein the resin film is a resin film made of a polar resin.