TW202225362A - Pressure-sensitive adhesive composition and layered film obtained using same - Google Patents

Abstract

Provided are a pressure-sensitive adhesive composition having an excellent effect in adhesive-force regulation and a layered film which includes a pressure-sensitive adhesive layer formed from the composition and is suitable for use as a surface-protective film. Specifically, the pressure-sensitive adhesive composition comprises a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1) and a pressure-sensitive adhesive (B).

Description

Adhesive composition and laminated film using the same

The present invention relates to an adhesive composition and a laminated film using the same.

In order to protect the surface of optical members such as polarizers, retardation plates, optical compensation films, and transparent conductive films used in liquid crystal displays, organic EL displays, touch panels, etc. during production, transportation, and use Adhesive protective film is attached to the surface, etc. The said protective film is a laminated body which consists of a transparent base material, such as polyethylene, polyester, polypropylene, and an adhesive bond layer, and it peels from the to-be-adhered body after completing the objective as a protective film.

When the protective film is peeled off from the adherend, it is required that it can be peeled off cleanly with a small force, and no adhesive residue (residual glue) is produced on the surface of the adherend. For optical members used in recent large-scale displays, mechanical peeling of surface protective films has become the mainstream, and peeling speeds often vary depending on the steps. Therefore, protective films with better peelability and less adhesive residue are required.

In response to the above-mentioned requirements, a surface protection film has been developed, which has both a micro-adhesive property that can be peeled off even with a slight force, and a re-peelability that can be peeled off cleanly even after being stuck once (for example, patent documents). 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2019-026707

[The problem to be solved by the invention]

The surface protective film used for the adhesive composition described in Patent Document 1 has a problem that the peeling performance is not sufficient because the adhesive force adjustment effect of the adhesive composition is insufficient. In addition, although the adhesive composition described in Patent Document 1 includes a compound having a fluorinated alkyl group having 6 carbon atoms, this compound is a compound that has concerns about environmental accumulation.

The problem to be solved by the present invention is to provide an adhesive composition and a laminated film; the adhesive composition is excellent in the effect of adjusting the adhesive force; the laminated film uses the adhesive composition in the adhesive layer, and can suitably Used as a surface protective film. [means to solve the problem]

As a result of intensive examination by the present inventors, they found that an adhesive composition comprising a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1) and an adhesive (B) can solve the above problems The subject has been solved and the present invention has been completed.

That is, the present invention relates to an adhesive composition comprising a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1) and an adhesive (B). [Effect of invention]

According to the present invention, an adhesive composition and a laminated film can be provided; the adhesive composition has excellent adhesive force adjustment effect; the laminated film uses the adhesive composition in an adhesive layer, and can be suitably used as a surface protection film use.

[Form for carrying out the invention]

Hereinafter, one embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented by adding appropriate changes within a range that does not impair the effects of the present invention. In addition, in this application specification, "(meth)acrylate" means one or both of acrylate and methacrylate.

<Adhesive composition> The adhesive composition of the present invention contains a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1), and an adhesive (B). The perfluoropolyether compound (A) can function as an adhesive force modifier, and by using the adhesive composition of the present invention, a laminated film excellent in peeling performance can be produced. Hereinafter, each component contained in the adhesive composition of the present invention will be described.

[Perfluoropolyether compound (A)] The perfluoropolyether compound (A) has a poly(perfluoroalkylene ether) chain (a1). The poly(perfluoroalkylene ether) chain (a1) possessed by the compound (A) may include a structure in which a bivalent fluorinated hydrocarbon group and an oxygen atom are alternately linked, and are represented by the following general formula (a1-1). Show the base.

(前述式(a1-1)中， X係各自獨立為全氟伸烷基， n1為重複個數。)

(In the aforementioned formula (a1-1), X is each independently a perfluoroalkylene group, and n1 is the number of repetitions.)

Among the plurality of Xs, two or more types of perfluoroalkylene groups may be present randomly or in blocks.

As the perfluoroalkylene group of X, the following perfluoroalkylene groups (X-1) to (X-6) can be exemplified.

The perfluoroalkylene group of X is preferably a perfluoroalkylene group having 1 to 3 carbon atoms, more preferably a perfluoromethylene group or a perfluoroethylidene group. Considering the industrial availability, more preferably Preferably, the perfluoromethylene group and the perfluoroethylene group coexist. In the case where the aforementioned perfluoromethylene group (X-1) and perfluoroethylene group (X-2) coexist, the presence ratio (X-1/X-2) (number ratio) is preferably 1/10～ 10/1, more preferably 3/10 to 10/3.

The number of repetitions of n1 is, for example, an integer in the range of 1-300, preferably an integer in the range of 2-200, more preferably an integer in the range of 3-100, further preferably an integer in the range of 6-70, most preferably The integer in the range of 12-50 is preferable.

The fluorine atoms contained in one poly(perfluoroalkylene ether) chain (a1) are preferably in the range of 18 to 200 atoms in total, and more preferably in the range of 25 to 150 atoms in total.

The content ratio of the poly(perfluoroalkylene ether) chain (a1) of the compound (A) is, for example, in the range of 1 to 90% by mass, preferably in the range of 1 to 80% by mass, and more preferably in the range of 1 to 70% by mass range. The content ratio of the poly(perfluoroalkylene ether) chain (a1) can be calculated and adjusted based on the feed amount of the polymerizable monomer having the poly(perfluoroalkylene ether) chain (a1) described later.

The compound (A) preferably has a polyoxyalkylene chain (a2) and/or a polysiloxane chain (a3). The compound (A) has a polyoxyalkylene chain (a2) and/or a polysiloxane chain (a3), thereby improving the adhesion adjustment function.

The polyoxyalkylene chain (a2) possessed by the compound (A) has a carbon number of 1 as long as a plurality of polyoxyethylene, polyoxypropylidene, polyoxybutylene, etc. can be formed by an ether bond. The alkylextended chains of to 6 may be linked together, and the structure of the alkylextended chains may be linear or branched.

As a polyoxyalkylene chain (a2) which a compound (A) has, the group represented by following formula (a2-1) is mentioned.

(前述式(a2-1)中， 複數個R ^a2係各自獨立為碳原子數1～6之伸烷基， n2為重複個數。)

(In the aforementioned formula (a2-1), a plurality of R ^a2 are each independently an alkylene group having 1 to 6 carbon atoms, and n2 is the number of repetitions.)

In a plurality of R ^a2 , two or more kinds of alkylene groups may be present randomly or in blocks.

The polyoxyalkylene chain (a2) is preferably a polyoxyethylene chain and/or a polyoxypropylidene chain, more preferably a polyoxyethylene chain. In the case where the polyoxyalkylene chain (a2) includes a polyoxyethylene chain and a polyoxypropylidene chain, the polyoxyethylene chain and the polyoxypropylidene chain in the polyoxyalkylene chain (a2) It may exist randomly, or it may exist in a block form.

The repetition number of n2 is, for example, an integer in the range of 1-200, preferably an integer in the range of 2-100, more preferably an integer in the range of 2-50, and still more preferably an integer in the range of 3-50.

The content ratio of the polyoxyalkylene chain (a2) of the compound (A) is, for example, in the range of 1 to 90% by mass, preferably in the range of 1 to 80% by mass, and more preferably in the range of 1 to 70% by mass. The content ratio of the polyoxyalkylene chain (a2) can be calculated and adjusted based on the feed amount of the polymerizable monomer having the polyoxyalkylene chain (a2) described later.

The polysiloxane chain (a3) which the compound (A) has includes a group represented by the following formula (a3-1).

(前述式(a3-1)中， 複數個R ^a3係各自獨立為碳原子數1～18之烷基或苯基， n3為重複個數。)

(In the aforementioned formula (a3-1), a plurality of R ^a3 are each independently an alkyl group or a phenyl group having 1 to 18 carbon atoms, and n3 is the number of repetitions.)

The alkyl group having 1 to 18 carbon atoms in R ^a3 may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and specific examples include methyl, ethyl, n-propyl, Isopropyl, n-butyl, tertiary butyl, n-hexyl, cyclohexyl, n-octyl, hexadecyl, etc. The alkyl group having 1 to 18 carbon atoms in R ^a3 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group.

The number of repetitions of n3 is, for example, an integer in the range of 1-200, preferably an integer in the range of 1-150.

The content ratio of the polysiloxane chain (a3) of the compound (A) is, for example, in the range of 1 to 90 mass %, preferably in the range of 1 to 80 mass %, and more preferably in the range of 1 to 70 mass %. The content ratio of the polysiloxane chain (a3) can be calculated and adjusted based on the feed amount of the polymerizable monomer having the polysiloxane chain (a3) described later.

The compound (A) is preferably a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1), and a polymerizable monomer having a polyoxyalkylene chain (a2) and a polymerizable monomer having a polysiloxane chain (a2). A copolymer in which at least one of the group consisting of the polymerizable monomers of the chain (a3) is used as a polymerization component. The "polymerization component" referred to here means a component constituting the copolymer, and does not include a solvent, a polymerization initiator, and the like that do not constitute the copolymer.

The term "polymerizable monomer" in the present invention means a compound having a polymerizable unsaturated group, and examples of the polymerizable unsaturated group include (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloyloxy group, ( C=C-containing groups such as meth)acryloylamide group, vinyl ether group, allyl group, styryl group, maleimide group, etc., preferably the following formula (U-1)～ The basis shown in (U-6).

The polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1), preferably a compound having a polymerizable unsaturated group at both ends of the poly(perfluoroalkylene ether) chain, more preferably a poly(perfluoroalkylene ether) chain A compound having a (meth)acryloyl or styryl group at both ends of a perfluoroalkylene ether) chain.

The molecular weight of the polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) is, for example, in the range of 300 to 50,000, preferably in the range of 300 to 30,000, and more preferably in the range of 300 to 10,000.

As a specific example of the compound which has a polymerizable unsaturated group at both terminals of a poly (perfluoroalkylene ether) chain, the compound represented by following formula (A1-1) - (A1-13) is mentioned. Moreover, PFPE in formula (A1-1) - (A1-13) is a linking group represented by said formula (a1-1).

The polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) used as a polymerization component may be used alone or in combination of two or more.

As a method for producing a compound having a polymerizable unsaturated group at both ends of a poly(perfluoroalkylene ether) chain, for example, a compound having one hydroxyl group at each end of a poly(perfluoroalkylene ether) chain can be mentioned. , a method obtained by subjecting (meth)acryloyl chloride to a dehydrochlorination reaction, a method obtained by subjecting (meth)acrylic anhydride to a reaction, a method obtained by subjecting (meth)acrylic acid to a dehydration reaction, and a method obtained by subjecting 2-( Meth)acryloyloxyethyl isocyanate obtained by urethane reaction, method obtained by esterification of Iconic anhydride, and styrene having chloromethyl group in the presence of a base A method obtained by reaction; esterification of 4-hydroxybutyl acrylate glycidylether with a compound having a carboxyl group at each end of a poly(perfluoroalkylene ether) chain A method obtained by reaction, a method obtained by esterification of glycidyl (meth)acrylate; a compound having one isocyanate group at each end of a poly(perfluoroalkylene ether) chain, so that (methyl) ) A method of reacting and introducing 2-hydroxyethyl acrylate, and a method of reacting 2-hydroxyethyl (meth)acrylamide (N-(2-hydroxyethyl)acrylamide). Among these, from the viewpoint of being easily available synthetically, a compound having one hydroxyl group at each end of the poly(perfluoroalkylene ether) chain is particularly preferable, and (meth)acryloyl chloride is subjected to a dehydrochlorination reaction A method obtained by reacting (meth)acrylic anhydride, or a method obtained by subjecting 2-(meth)acryloylethylethyl isocyanate to a urethanization reaction.

The polymerizable monomer having a polyoxyalkylene chain (a2) is preferably a compound represented by the following formula (A2-1) or a compound represented by the following formula (A2-2).

(前述式(A2-1)及(A2-2)中， R ^a21、R ^a22及R ^a23係各自獨立為碳原子數1～6之伸烷基， R ^a24係各自獨立為氫原子或甲基， R ^a25係氫原子或碳原子數1～6之烷基， p、q及r係各自獨立為0以上之整數，p＋q＋r為1以上之整數。)

(In the aforementioned formulas (A2-1) and (A2-2), R ^a21 , R ^a22 and R ^a23 are each independently an alkylene group having 1 to 6 carbon atoms, and R ^a24 is each independently a hydrogen atom or a methyl group , R ^a25 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, p, q and r are each independently an integer of 0 or more, and p+q+r is an integer of 1 or more.)

The alkylene group having 1 to 6 carbon atoms in R ^a21 , R ^a22 and R ^a23 is preferably an alkylene group having 2 to 4 carbon atoms.

p+q+r is, for example, an integer in the range of 1-200, preferably an integer in the range of 2-100, more preferably an integer in the range of 2-50, and still more preferably an integer in the range of 3-50.

The molecular weight of the polymerizable monomer having a polyoxyalkylene chain (a2) is, for example, in the range of 50 to 20,000, preferably in the range of 50 to 10,000, and more preferably in the range of 50 to 800.

Commercially available products can be used as the polymerizable monomer having a polyoxyalkylene chain (a2), and examples thereof include BLEMMER PE-90 and BLEMMER PE which are hydroxyl-terminated polyalkylene glycol mono(meth)acrylates -200, BLEMMER PE-350, BLEMMER AE-90, BLEMMER AE-200, BLEMMER AE-400, BLEMMER PP-1000, BLEMMER PP-500, BLEMMER PP-800, BLEMMER AP-150, BLEMMER AP-400, BLEMMER AP -550, BLEMMER AP-800, BLEMMER 50PEP-300, BLEMMER 70PEP-350B, BLEMMER AEP series, BLEMMER 55PET-400, BLEMMER 30PET-800, BLEMMER 55PET-800, BLEMMER AET series, BLEMMER 30PPT-800, BLEMMER 50PPT-800 , BLEMMER 70PPT-800, BLEMMER APT series, BLEMMER 10PPB-500B, BLEMMER 10APB-500B (above, manufactured by NOF Corporation); BLEMMER PME of alkyl-terminated polyalkylene glycol mono(meth)acrylate -100, BLEMMER PME-200, BLEMMER PME-400, BLEMMER PME-1000, BLEMMER PME-4000, BLEMMER AME-400, BLEMMER 50POEP-800B, BLEMMER 50AOEP-800B, BLEMMER PLE-200, BLEMMER ALE-200, BLEMMER ALE -800, BLEMMER PSE-400, BLEMMER PSE-1300, BLEMMER ASEP series, BLEMMER PKEP series, BLEMMER AKEP series, BLEMMER ANE-300, BLEMMER ANE-1300, BLEMMER PNEP series, BLEMMER PNPE series, BLEMMER 43ANEP-500, BLEMMER 70ANEP -550 (above, manufactured by NOF Corporation), LIGHT ESTER MC, LIGHT ESTER 130MA, LIGHT ESTER 041MA, LIGHT ACRYLATE BO-A, LIGHT ACRYLATE EC-A, LIGHT ACRYLATE MTG-A, LI GHT ACRYLATE 130A, LIGHT ACRYLATE DPM-A, LIGHT ACRYLATE P-200A, LIGHT ACRYLATE NP-4EA, LIGHT ACRYLATE NP-8EA (above, manufactured by Kyoeisha Chemical Co., Ltd.), etc.

The polymerizable monomer having a polyoxyalkylene chain (a2) used as a polymerization component may be used alone or in combination of two or more.

The polymerizable monomer containing the polysiloxane chain (a3) is preferably a compound represented by the following formula (A3-1).

(前述式(A3-1)中， R ^a31係各自獨立為碳原子數1～6之烷基或-OSi(R ^a34) ₃所示之基(R ^a34係各自獨立為碳原子數1～3之烷基)， R ^a32及R ^a33係各自獨立為碳原子數1～6之烷基， R ^a35係氫原子或甲基， L ¹係碳原子數1～50之伸烷基或碳原子數1～50之伸烷基氧基， n3為重複個數。)

(In the aforementioned formula (A3-1), R ^a31 is each independently an alkyl group having 1 to 6 carbon atoms or a group represented by -OSi(R ^a34 ) ₃ (R ^a34 is each independently an alkyl group having 1 to 3 carbon atoms) R ^a32 and R ^a33 are each independently an alkyl group with 1 to 6 carbon atoms, R ^a35 is a hydrogen atom or a methyl group, and L ¹ is an alkylene group with 1 to 50 carbon atoms or a carbon atom number 1-50 alkyleneoxy groups, n3 is the number of repetitions.)

R ^a31 , R ^a32 and R ^a34 are preferably methyl groups. R ^a33 is preferably butyl. The number of repetitions of n3 is, for example, in the range of 1-200, preferably in the range of 1-150.

The alkylene group having 1 to 50 carbon atoms in L ¹ is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, further preferably a methylene group, a Ethyl, n-propyl or isopropyl.

The alkyleneoxy group having 1 to 50 carbon atoms in L ¹ is, for example, a group in which one -CH ₂ - in the aforementioned alkylene group having 1 to 50 carbon atoms is substituted with -O-. The alkyleneoxy group having 1 to 50 carbon atoms in L ¹ is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and even more preferably is methyleneoxy, ethylideneoxy, propylideneoxy, oxytrimethylene, butyleneoxy, oxytetramethylene, pentyleneoxy, heptyloxy or Extended octyloxy.

The carbon atoms constituting the alkylene with 1 to 50 carbon atoms and the alkyleneoxy group with 1 to 50 carbon atoms respectively constituting L ¹ may also be substituted with one or more substituents such as hydroxyl, phenyl, and phenoxy. .

As the polymerizable monomer containing the polysiloxane chain (a3), compounds represented by the following formulae (A3-2) to (A3-9) are preferred.

(前述式(A3-2)～(A3-9)中， m係各自獨立為1～6之整數。 n3係重複個數，例如1～200的範圍，較佳為1～150的範圍。 R ^a32係各自獨立為碳原子數1～6之烷基。 R ^a33係各自獨立為碳原子數1～6之烷基。 R ^a35係各自獨立為氫原子或甲基。)

(In the aforementioned formulas (A3-2) to (A3-9), m is each independently an integer of 1 to 6. n3 is the number of repetitions, for example, in the range of 1 to 200, preferably in the range of 1 to 150. R ^a32 is each independently an alkyl group having 1 to 6 carbon atoms. R ^a33 is each independently an alkyl group having 1 to 6 carbon atoms. R ^a35 is each independently a hydrogen atom or a methyl group.)

The molecular weight of the polymerizable monomer including the polysiloxane chain (a3) is, for example, in the range of 400 to 30,000, preferably in the range of 400 to 20,000, and more preferably in the range of 400 to 15,000.

A commercial item can be used for the polymerizable monomer containing a polysiloxane chain (a3).

The polymerizable monomer containing the polysiloxane chain (a3) used as a polymerization component may be used alone or in combination of two or more.

The compound (A) may also contain a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1), a polymerizable monomer having a polyoxyalkylene chain (a2), and a polymerizable monomer having a polysiloxane chain (a3) Other polymerizable monomers other than the polymerizable monomers are used for the polymerization components.

As said other polymerizable monomer, the polymerizable monomer which has a C1-C18 alkyl group (a4), the C6-C18 aromatic group (a5), etc. are mentioned.

The alkyl group (a4) having 1 to 18 carbon atoms may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and specific examples thereof include methyl, ethyl, n-propyl, Isopropyl, n-butyl, tertiary butyl, n-hexyl, cyclohexyl, n-octyl, hexadecyl, etc.

The alkyl group (a4) having 1 to 18 carbon atoms may be substituted with one or more substituents such as a hydroxyl group, a phenyl group, and a phenoxy group. The alkyl group (a4) having 1 to 18 carbon atoms includes, for example, a hydroxyalkyl group having 1 to 18 carbon atoms, a phenylalkyl group having 7 to 18 carbon atoms, and a phenoxyalkyl group having 7 to 18 carbon atoms.

Examples of the aromatic group (a5) having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, an anthracene-1-yl group, and a phenanthren-1-yl group. The aromatic group (a5) having 6 to 18 carbon atoms may be substituted with a substituent such as a hydroxyl group, an alkyl group, or an alkoxy group, and includes, for example, a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms.

Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and having a (meth)acryloyl group as the polymerizable unsaturated group include methyl (meth)acrylate and ethyl (meth)acrylate. ester, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, secondary butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylate base) tertiary butyl acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2- (meth)acrylate Carbon atom of (meth)acrylic acid such as ethylhexyl, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, etc. Alkyl esters with numbers from 1 to 18; (meth)acrylate (dicyclopentanyloxylethyl (meth)acrylate), (meth)acrylate (isobornyloxylethyl (meth)acrylate) , Isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, ( Bridged cyclic alkyl esters having 1 to 18 carbon atoms of (meth)acrylic acid such as dicyclopentenyl (meth)acrylate and the like.

Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and having a polymerizable unsaturated group that is a vinyl ether group include methyl vinyl ether, ethyl vinyl ether, and n-propyl vinyl. Ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tertiary butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether , n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, etc. alkyl vinyl ether, cycloalkyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxy Propyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 1-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 1-Hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 3-hydroxy-2-methylpropyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexane-1,4-dimethanol monovinyl ether, etc.

Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and having an allyl group as the polymerizable unsaturated group include, for example, 2-hydroxyethyl allyl ether and 4-hydroxybutyl allyl group. ether, glycerol monoallyl ether, etc.

啉等。As the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and having a (meth)acryloylamide group as the polymerizable unsaturated group, for example, N,N-dimethylacrylamide, N,N-Diethylacrylamide, N-isopropylacrylamide, Diacetoneacrylamide, Acrylamide

Lin et al.

Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and wherein the polymerizable unsaturated group is a maleimide group include methylmaleimide and ethylmaleimide. , propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, Cyclohexylmaleimide, etc.

Examples of the polymerizable monomer having a hydroxyalkyl group having 1 to 18 carbon atoms and having a polymerizable unsaturated group as a (meth)acryloyl group include, for example, 2-hydroxyethyl (meth)acrylate, (meth)acrylate base) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, (meth)acrylate base) 2,3-dihydroxypropyl acrylate, etc.

Examples of polymerizable monomers having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms, and wherein the polymerizable unsaturated group is a (meth)acryloyl group, include, for example. : Benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate esters, etc.

As a polymerizable monomer which has a C6-C18 aromatic group, styrene, alpha-methylstyrene, p-methylstyrene, p-methoxystyrene, etc. are mentioned, for example.

The aforementioned other monomers used as the polymerization component may be used alone or in combination of two or more.

Compound (A) is a polymerizable monomer other than a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) and a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) (a polymerizable monomer having a polyoxyalkylene chain (a2), a polymerizable monomer having a polysiloxane chain (a3), and any other polymerizable monomer) as the polymer component of the copolymer, the The polymerization form is not particularly limited. The above-mentioned copolymer may be, for example, any of random copolymers, block copolymers, alternating copolymers, graft copolymers, and the like.

The feed ratio of each of the above-mentioned polymerizable monomers is not particularly limited. The amount of the polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) is, for example, in the range of 1 to 90% by mass, preferably in the range of 1 to 80% by mass, and more preferably in the range of 1 to 90% by mass of the entire polymer component. 70% by mass range.

The compound (A) is a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1), and is selected from the group consisting of a polymerizable monomer including a polyoxyalkylene chain (a2) and a polysiloxane chain ( When one or more of the group consisting of the polymerizable monomer of a3) is used as a copolymer of the polymerizable component, with respect to 100 parts by mass of the polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1), The total of the polymerizable monomer containing the polyoxyalkylene chain (a2) and the polymerizable monomer containing the polysiloxane chain (a3) is, for example, in the range of 5 to 2,000 parts by mass, preferably 10 to 2,000 parts by mass range, more preferably in the range of 15 to 2,000 parts by mass.

The compound (A) preferably contains a poly(perfluoroalkylene ether) chain (a1) on the main chain and a polyoxyalkylene chain (a2) and/or a polysiloxane chain (a3) on the side chain. polymer. The "main chain" here means the longest molecular chain among the molecular chains constituting the compound (A), and the "side chain" means molecular chains other than the main chain.

The compound (A) is preferably a polymerizable monomer having a polymerizable unsaturated group at both ends of the poly(perfluoroalkylene ether) chain (a1), and is preferably selected from the group consisting of a polyoxyalkylene chain (a2) A copolymer in which one or more of the group consisting of a polymerizable monomer and a polymerizable monomer including a polysiloxane chain (a3) are used as a polymerization component.

The compound (A) preferably does not have a perfluoroalkyl group having 6 or more carbon atoms. The compound (A) can reduce environmental load by not containing a perfluoroalkyl group having 6 or more carbon atoms. In addition, the "perfluoroalkyl group having 6 or more carbon atoms" referred to here does not contain a poly(perfluoroalkylene ether) chain.

Compound (A) preferably does not have a fluorinated alkyl group. Since the compound (A) does not have a fluorinated alkyl group, compatibility with the matrix resin can be ensured.

The weight-average molecular weight of the compound (A) is not particularly limited, but from the viewpoints of compatibility with the adhesive (B) described later, ease of adjustment of the adhesive force, and reduction of residual glue, etc. The range of 3,000 to 300,000 is preferable, the range of 3,000 to 200,000 is more preferable, and the range of 4,000 to 100,000 is preferable from the viewpoint of the uniformity of peeling force when used as a surface protection film of a large-area optical member or the like. The weight average molecular weight in the present invention is a value measured according to the method described in Examples.

The production method of the compound (A) is not particularly limited, and it can be produced by a known method. The compound (A) can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, etc., according to a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, etc., especially a radical polymerization method. , which is simple and industrially preferred. For example, it can be produced by adding a general-purpose radical polymerization initiator to an organic solvent and polymerizing a polymerizable monomer mixture. Depending on the polymerizable monomer to be used, a dropping polymerization method or the like in which the polymer monomer and the initiator are added dropwise to the reaction vessel for polymerization is also effective for obtaining a copolymer having a uniform composition.

As the above-mentioned polymerization initiator, various polymerization initiators can be used, and examples thereof include peroxides such as benzyl peroxide and dioxygen peroxide, azobisisobutyronitrile, and dimethyl azobisisobutyrate. , azo compounds such as benzoazotriphenylmethane, metal chelates such as Mn(acac) ₃ , transition metal catalysts that cause living radical polymerization, etc. According to needs, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, octylthioglycolic acid, etc. can also be used, or as additives such as chain transfer agents Thiol compounds with coupling groups such as γ-mercaptopropyl trimethoxysilane.

The polymerization may be performed in the presence or absence of a solvent, but it is preferably performed in the presence of a solvent from the viewpoint of workability. Examples of the solvent used in the polymerization include alcohols such as ethanol, isopropanol, n-butanol, isobutanol, and tertiary butanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketones such as methyl amyl ketone; esters of methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, etc.; methyl 2-oxypropionate, 2- Ethyl oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Monocarboxylates such as propyl methoxypropionate and butyl 2-methoxypropionate; polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, etc.; methyl methacrylate Ethers of base silosu, serosol, butyl serosol, butyl carbitol, ethyl serosol acetate, etc.; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycols such as acetate and propylene glycol monobutyl ether acetate and their esters; halogen solvents such as 1,1,1-trichloroethane and chloroform; ethers such as tetrahydrofuran and diethylene; benzene, Aromatics such as toluene and xylene; and fluorinated inert liquids such as perfluorooctane and perfluorotri-n-butylamine. These solvents may be used alone or in combination of two or more. The solvent used for the polymerization of the compound (A) can be used as the solvent of the adhesive composition of the present invention.

[Adhesive (B)] The adhesive (B) can be used without particular limitation as long as it has adhesiveness, and examples thereof include acrylic adhesives, urethane-based adhesives, synthetic rubber-based adhesives, and natural rubber-based adhesives. , polysiloxane adhesives, etc. Among these adhesives, it is preferable to use an acrylic adhesive (b1) and/or a urethane adhesive (b2).

The (meth)acrylic polymer constituting the acrylic adhesive (b1) can be obtained from a raw material monomer using a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms as a main component monomer . The said (meth)acrylic-type monomer can use 1 type or 2 or more types as a main component. By using the aforementioned (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, it becomes easy to control the adhesive force to the adherend (to be protected) at a low level, and it is possible to obtain A surface protection film with excellent light peelability and repeelability. In addition, the "main component" in the present invention means the component with the largest amount in the total amount of the constituent components, and the "main component" is preferably more than 40% by mass, more preferably more than 50% by mass, and still more preferably more than 60% by mass. quality%.

Examples of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate. , tertiary butyl (meth)acrylate, tertiary butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, (meth)acrylic acid Isodecyl ester, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, etc.

Among the above-mentioned (meth)acrylic monomers, from the viewpoint that it becomes easy to control the adhesive force to the adherend at a low level and is excellent in releasability, (methyl) ) Hexyl acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, iso-octyl (meth)acrylate Nonyl ester, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate Such as (meth)acrylic monomers having an alkyl group having 6 to 14 carbon atoms.

It is preferable to contain 50 mass % or more of (meth)acrylic monomers having an alkyl group having 1 to 14 carbon atoms with respect to the total amount of 100 mass % of the monomer components constituting the (meth)acrylic polymer. , more preferably 60 mass % or more, still more preferably 70 to 99 mass %, and most preferably 80 to 97 mass %.

The (meth)acrylic polymer constituting the acrylic adhesive (b1) preferably contains a (meth)acrylic monomer having a hydroxyl group as a raw material monomer. As a (meth)acrylic-type monomer which has the said hydroxyl group, 1 type or 2 or more types can be used.

By using the aforementioned (meth)acrylic monomer having a hydroxyl group, it becomes easy to control the crosslinking of the adhesive composition, etc., and then it becomes easy to control the improvement of the wettability due to the flow and the reduction of the adhesive force during peeling. The balance between them is also preferable from the viewpoint of antistatic.

As (meth)acrylic-type monomer which has the said hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate are mentioned, for example , 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (meth)acrylic acid (4-Methylolcyclohexyl) methyl ester, N-Methylol (meth)acrylamide and the like. In particular, by using a (meth)acrylic monomer having a hydroxyl group and having an alkyl group of 4 or more carbon atoms, light peeling during high-speed peeling can be facilitated, which is preferable.

It is preferable to contain 15 parts by mass or less of the (meth)acrylic monomer having a hydroxyl group with respect to 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, more preferably It is 1-13 mass parts, More preferably, it is 2-10 mass parts, Most preferably, it is 3-8 mass parts. Within the aforementioned range, it becomes easy to control the balance between the wettability of the adhesive composition and the cohesive force of the obtained adhesive layer, which is preferable.

Since it is easy to achieve a balance of adhesive properties, a polymerizable monomer for adjusting the glass transition temperature and peelability of the (meth)acrylic polymer can be used as other polymerizable monomer components, and the Tg can be made 0°C or lower. (usually above -100°C).

Polymerization other than the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms and the (meth)acrylic monomer having a hydroxyl group used in the (meth)acrylic polymer As the monomer, a (meth)acrylic monomer having a carboxyl group can be used.

As a (meth)acrylic-type monomer which has the said carboxyl group, (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, etc. are mentioned, for example.

The (meth)acrylic monomer having a carboxyl group is preferably 5 parts by mass or less, more preferably 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms. 3 parts by mass or less, more preferably less than 1 part by mass, still more preferably less than 0.2 part by mass, and most preferably not less than 0.01 part by mass and less than 0.1 part by mass. Within the aforementioned range, the adhesive force can be prevented from increasing with time (adhesive force increase preventing property), which is preferable.

The (meth)acrylic monomer having a hydroxyl group and the (meth)acrylic monomer having a carboxyl group may be used in combination for the purpose of achieving both the peeling charge characteristic and the adhesion increase prevention property.

啉、乙烯基醚單體等。其中，較佳為使用含有氰基的單體、含有醯胺基的單體、含有亞醯胺的單體、含有胺基的單體、及N-丙烯醯基

啉等含有氮的單體。藉由使用含有氮的單體，由於可確保不產生浮起與剝落等之適當的黏著力，進一步能得到剪切力優良之表面保護薄膜，故為有用的。此等聚合性單體，可單獨使用，也可混合2種以上單體使用。Further, as the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the (meth)acrylic monomer having a hydroxyl group, and the (meth)acrylic monomer having a hydroxyl group used in the (meth)acrylic polymer Other polymerizable monomers other than the (meth)acrylic monomer of the carboxyl group can be used without any particular limitation. Components with functional groups that can improve adhesion and serve as cross-linking points can be appropriately used, such as: cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, etc. Amine group-containing monomer, imide group-containing monomer, amine group-containing monomer, epoxy group-containing monomer, N-acrylamide group

Linen, vinyl ether monomers, etc. Among them, it is preferable to use a cyano group-containing monomer, an amide group-containing monomer, an imide group-containing monomer, an amine group-containing monomer, and an N-acryloyl group

Nitrogen-containing monomers such as phenoline. By using a nitrogen-containing monomer, it is useful because it is possible to secure a suitable adhesive force that does not cause floating and peeling, and further to obtain a surface protection film excellent in shear force. These polymerizable monomers may be used alone or in combination of two or more.

As said cyano group containing monomer, acrylonitrile and methacrylonitrile are mentioned, for example.

As said vinyl ester monomer, vinyl acetate, vinyl propionate, vinyl laurate, etc. are mentioned, for example.

As said aromatic vinyl monomer, styrene, chlorostyrene, chloromethylstyrene, alpha-methylstyrene, other substituted styrene, etc. are mentioned, for example.

Examples of the aforementioned amide group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N,N-Dimethylmethacrylamide, N,N-Diethylacrylamide, N,N-Diethylmethacrylamide, N,N'-Methylenebisacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, diacetone acrylamide, etc.

Examples of the above-mentioned imide-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, iconimide, and the like.

Examples of the aforementioned amino group-containing monomer include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and N,N-dimethyl (meth)acrylate. aminopropyl ester, etc.

As a monomer of the said epoxy group, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, allyl glycidyl ether, etc. are mentioned, for example.

As said vinyl ether monomer, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc. are mentioned, for example.

With respect to 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, and the (meth)acrylic monomer having a hydroxyl group The (meth)acrylic monomer and other polymerizable monomers other than the (meth)acrylic monomer having a carboxyl group are preferably from 0 to 40 parts by mass, from the viewpoint of being able to appropriately adjust good releasability. Preferably it is 0-30 mass parts.

The aforementioned (meth)acrylic polymer may further contain a polyoxyalkylene chain-containing reactive monomer as a monomer component.

The average c of the oxyalkylene units of the reactive monomer containing the polyoxyalkylene chain is preferably 1 to 40, more preferably 3 to 40, further preferably 4 to 35, particularly preferably 5 ~30. When the average number of added molars is 1 or more, the effect of reducing the contamination of the adherend (to-be-protected body) tends to be efficiently obtained. Moreover, in the case where the above-mentioned average added molar ratio is larger than 40, the viscosity of the adhesive composition tends to increase, making coating difficult. In addition, the terminal of the oxyalkylene chain may be directly a hydroxyl group, or may be substituted with other functional groups or the like.

The reactive monomer containing the polyoxyalkylene chain may be used alone or in a mixture of two or more, and the total content thereof is preferably the total of the monomer components of the (meth)acrylic polymer. 20 mass % or less of the amount, more preferably 10 mass % or less, still more preferably 5 mass % or less, still more preferably 4 mass % or less, particularly preferably 3 mass % or less, still more preferably 1 mass % the following.

Examples of the oxyalkylene unit of the reactive monomer containing the polyoxyalkylene chain include those having 1 to 6 carbon atoms, and examples thereof include oxymethylene and oxyethylene. , oxypropylene, oxybutylene, etc. The hydrocarbon group of the oxyalkylene chain may be straight or branched.

The aforementioned reactive monomer containing a polyoxyalkylene chain is more preferably a reactive monomer having an oxirane group. By using a (meth)acrylic polymer containing a reactive monomer having an ethylene oxide group as a matrix polymer, the compatibility between the matrix polymer and the perfluoropolyether compound (A) is improved, and it is possible to appropriately Exudation to the adherend is suppressed, making it easy to obtain an adhesive composition with low contamination.

Examples of the reactive monomers containing the polyoxyalkylene chain include (meth)acrylic acid alkylene oxide adducts, compounds having an acryl group, a methacryloyl group, an allyl group, and the like in the molecule. Reactive surfactants of reactive substituents, etc.

Specific examples of the above-mentioned (meth)acrylic acid alkylene oxide adduct include, for example, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol-polypropylene glycol (methyl) base) acrylate, polyethylene glycol-polybutylene glycol (meth)acrylate, polypropylene glycol-polybutylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethylene glycol Oxy polyethylene glycol (meth)acrylate, butoxy polyethylene glycol (meth)acrylate, octoxy polyethylene glycol (meth)acrylate, lauryloxy polyethylene glycol (methyl) base) acrylate, stearyloxy polyethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, octoxypolyethylene glycol (meth)acrylate Ethylene glycol-polypropylene glycol (meth)acrylate, etc.

Moreover, as a specific example of the said reactive surfactant, for example, an anionic reactive surfactant having a (meth)acryloyl group or an allyl group, a nonionic reactive surfactant, a cationic reactive surfactant can be mentioned. surfactants, etc.

The weight average molecular weight (Mw) of the (meth)acrylic polymer constituting the acrylic adhesive (b1) is preferably 100,000 to 5,000,000, more preferably 200,000 to 2,000,000, and still more preferably 300,000 to 800,000. When the weight-average molecular weight is larger than 100,000, the cohesive force of the adhesive layer becomes suitable and there is a tendency to suppress residual adhesive. On the other hand, when the weight-average molecular weight is 5 million or less, the fluidity of the polymer is appropriate, and the wetting of the adherend is sufficient, and the occurrence of the adhesion between the adherend and the adhesive layer of the surface protective film can be suppressed. Blistering occurs. In addition, the said weight average molecular weight means what was measured by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the (meth)acrylic polymer constituting the acrylic adhesive (b1) is preferably 0°C or lower, more preferably -10°C or lower (usually -100°C or higher). When the glass transition temperature is higher than 0° C., the polymer does not flow easily, and the wetting tends to become insufficient. In particular, by making the glass transition temperature -61°C or lower, it becomes easy to obtain an adhesive layer excellent in wettability and light peelability. Moreover, the glass transition temperature of a (meth)acrylic-type polymer can be adjusted in the said range by suitably changing the monomer component and composition ratio used.

The polymerization method of the aforementioned (meth)acrylic polymer is not particularly limited, and can be polymerized by well-known methods such as solution polymerization, emulsion polymerization, block polymerization, and suspension polymerization. In terms of properties such as low contamination of the adherend (protected body), solution polymerization is more preferable. Moreover, the polymer obtained may be any of random copolymers, block copolymers, alternating copolymers, graft copolymers, and the like.

In the case of using the urethane-based adhesive (b2) as the adhesive (B), any suitable urethane-based adhesive can be used. Preferable examples of the urethane-based adhesive (b2) include those composed of a urethane resin (urethane-based polymer) obtained by reacting a polyol and a polyisocyanate compound. . As said polyol, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, etc. are mentioned, for example. As said polyisocyanate compound, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, etc. are mentioned, for example.

In the case of using a polysiloxane-based adhesive in the aforementioned adhesive layer, any suitable polysiloxane-based adhesive can be used. As such a polysiloxane-based adhesive, it is preferable to use a polysiloxane resin (polysiloxane-based polymer, a polysiloxane component) or a polysiloxane resin (polysiloxane-based polymer, polysiloxane-based polymer, polysiloxane component) obtained by agglutination.

Moreover, as said polysiloxane type adhesive agent, an addition reaction hardening type polysiloxane type adhesive agent and a peroxide hardening type polysiloxane type adhesive agent are mentioned. Among these polysiloxane-based adhesives, since no peroxide (benzyl peroxide, etc.) is used and no decomposition products are generated, addition reaction-curable polysiloxane-based adhesives are preferred.

As the curing reaction of the above-mentioned addition reaction-curable polysiloxane-based adhesive, for example, in the case of obtaining a polyalkyl silicone-based adhesive, polyalkylhydrogen silicone A method of hardening an oxane composition.

In the adhesive composition of the present invention, the blending ratio of the perfluoropolyether compound (A) and the adhesive (B) may be appropriately set according to the desired adhesive force. When the adhesive composition of the present invention is used in the adhesive layer of the surface protective film, the content of the perfluoropolyether compound (A) is preferably 0.01 to 20 mass % in the solid content of the adhesive composition , more preferably 0.1 to 5.0 mass %. Within this range, the perfluoropolyether compound (A) can sufficiently function as an adhesive force modifier. In addition, in this invention, "solid content" means the component after removing a solvent from an adhesive composition.

[other ingredients] The adhesive composition of the present invention only needs to contain the perfluoropolyether compound (A) and the adhesive (B), and may optionally contain other components such as various additives within a range that does not impair the effects of the present invention.

The adhesive composition of the present invention preferably contains a crosslinking agent as another component. For example, when the adhesive composition of the present invention contains the aforementioned (meth)acrylic polymer as the adhesive (B), the aforementioned (meth)acrylic polymer is appropriately adjusted by further including a crosslinking agent. The composition unit, composition ratio, selection of cross-linking agent and addition ratio, etc. are then cross-linked, and an adhesive layer with better heat resistance can be easily obtained.

As the crosslinking agent, isocyanate compounds, epoxy compounds, melamine-based resins, aziridine derivatives, metal chelate compounds, etc. can also be used, and it is particularly preferable to use isocyanate compounds. In addition, these compounds may be used individually or in mixture of 2 or more types.

三酮鍵等改性而成的多異氰酸酯改質體。 作為前述異氰酸酯化合物的市售品，可列舉例如：商品名Takenate 300S、Takenate 500、Takenate 600、Takenate D165N、Takenate D178N(以上為武田藥品工業公司製)、Sumidur T80、Sumidur L、Desmodur N3400(以上為Sumika Bayer Urethane公司製)、Millionate MR、Millionate MT、Coronate L、Coronate HL、Coronate HX(以上為Nippon Polyurethane Industry Co.,Ltd.製)等。 此等異氰酸酯化合物可單獨使用，也可混合2種以上使用，也能合併2官能的異氰酸酯化合物與3官能以上的異氰酸酯化合物使用。藉由混合2種以上交聯劑使用，能兼顧黏著性與抗反彈性(對曲面的接著性)，可得到接著可靠度更優良的積層薄膜。 Examples of the isocyanate compound include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate, and cyclopentylene diisocyanate. Alicyclic isocyanates such as isocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, stubble isocyanate (XDI) ) and other aromatic isocyanates, and these isocyanate compounds are passed through an allophanate bond, a biuret bond, a trimeric isocyanate bond, a uretdione bond, a urea bond, a carbodiimide bond, a uretonidene bond Amine (uretonimine) bond, 㗁two

A modified polyisocyanate modified with triketone bonds, etc. Examples of commercially available products of the aforementioned isocyanate compounds include trade names Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (the above are manufactured by Takeda Pharmaceutical Co., Ltd.), Sumidur T80, Sumidur L, and Desmodur N3400 (the above are Sumika Bayer Urethane Co., Ltd.), Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (the above are manufactured by Nippon Polyurethane Industry Co., Ltd.), and the like. These isocyanate compounds may be used alone or in combination of two or more, and may be used in combination of a bifunctional isocyanate compound and a trifunctional or more isocyanate compound. By mixing two or more types of cross-linking agents, both adhesion and rebound resistance (adhesion to curved surfaces) can be achieved, and a laminated film with better adhesion reliability can be obtained.

Examples of the epoxy compound include N,N,N',N'-tetraglycidyl-m-xylylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 1,3-bis( N,N-diglycidylaminomethyl)cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like.

As said melamine type-resin, hexamethylol melamine etc. are mentioned. As said aziridine derivative, the brand name HDU, TAZM, and TAZO (the above are made by Mutual Pharmaceutical Co., Ltd.) which are commercially available products, etc. are mentioned, for example.

Examples of the metal chelate compound include aluminum, iron, tin, titanium, nickel and the like as metal components, and acetylene, methyl acetoacetate, ethyl lactate and the like as chelate components.

The content of the crosslinking agent is, for example, preferably 0.01 to 20 parts by mass, and more preferably 0.1 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer used for the acrylic adhesive (b1). To 15 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 1.0 to 6 parts by mass. By using the crosslinking agent within this range, the cohesive force of the obtained adhesive layer is suitable, sufficient heat resistance is easily obtained, and adhesive residue can be suppressed. A crosslinking agent may be used individually by 1 type, or may be used in mixture of 2 or more types.

The adhesive composition may contain a cross-linking catalyst in order to carry out any of the above-mentioned cross-linking reactions more efficiently. As the above-mentioned crosslinking catalyst, for example, tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, ginseng(acetylacetone)iron, ginseng(hexan-2,4-dione) can be used. Iron, ginseng (heptane-2,4-dione) iron, ginseng (heptane-3,5-dione) iron, ginseng (5-methylhexan-2,4-dione) iron, ginseng (octane-2) ,4-dione) iron, ginseng (6-methylhept-2,4-dione) iron, ginseng (2,6-dimethylhept-3,5-dione) iron, ginseng (nonan-2 ,4-dione)iron, ginseng (nonan-4,6-dione)iron, ginseng (2,2,6,6-tetramethylhept-3,5-dione)iron, ginseng (tridecane) -6,8-Diketone) iron, ginseng (1-phenylbutan-1,3-dione) iron, ginseng (hexafluoroacetone) iron, ginseng (ethyl acetone) iron, ginseng (ethyl acetate) N-Propyl Acetate) Iron Ester) iron, ginseng (methyl acetonitrile) iron, ginseng (acetate ethyl acetate) iron, ginseng (n-propyl acetate) iron, ginseng (isopropyl acetate) iron, ginseng (propionyl acetate) iron n-Butyl acetate) iron, ginseng (tertiary butyl acetate propyl acetate) iron, ginseng (tertiary butyl acetate tertiary butyl acetate) iron, ginseng (benzyl acetate) iron, ginseng (malonate) Iron-based catalysts such as dimethyl)iron, gins(diethyl)iron, trimethoxyiron, triethoxyiron, triisopropoxyiron, and ferric chloride. These crosslinking catalysts may be used alone or in combination of two or more.

Although content of the said crosslinking catalyst is not specifically limited, For example, it is preferable that it is about 0.0001-1 mass part with respect to 100 mass parts of said (meth)acrylic-type polymers, More preferably, it is 0.001-0.5 mass part. Within the above-mentioned range, the rate of the crosslinking reaction when the adhesive layer is formed is high, and the pot life of the adhesive composition becomes longer, which is a preferable aspect.

<Laminated film> The laminated film of this invention has an adhesive layer and a base material layer, and the said adhesive layer is a layer formed using the adhesive composition of this invention. The laminated film of the present invention can be produced by coating and crosslinking the adhesive composition of the present invention on at least one side of the base material layer. In addition, the laminated film of the present invention can also be produced by transferring the adhesive layer preliminarily crosslinked with the adhesive composition of the present invention to at least one side of the base material layer.

The method of forming the adhesive layer on the substrate layer is not particularly limited, for example: by coating the adhesive composition (solution) of the present invention on the substrate, and then drying and removing the polymerization solvent, etc., the adhesive layer is formed on the substrate agent layer to make. Then, aging may be performed for the purpose of adjustment of component transfer of the adhesive layer, adjustment of cross-linking reaction, and the like. When the adhesive composition is applied on a substrate to produce a laminated film, one or more solvents other than the polymerization solvent may be newly added to the adhesive composition so that the adhesive composition can be uniformly coated on the substrate layer.

As a method for forming an adhesive layer in the production of the laminated film of the present invention, a known method used for the production of tapes can be used. Specifically, for example, roll coating, gravure coating, reverse roll coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like can be mentioned.

The laminated film of the present invention is usually prepared so that the thickness of the adhesive layer is about 1 to 200 μm, preferably about 3 to 100 μm. When the thickness of the adhesive layer is within this range, it is easy to obtain an appropriate balance between re-peelability and adhesiveness, which is preferable.

The total thickness of the laminated film of the present invention is preferably 1 to 400 μm, more preferably 10 to 200 μm, and most preferably 20 to 150 μm. When the total thickness of the laminated film is within this range, the adhesive properties (removability, adhesiveness, etc.), workability, and appearance properties are excellent, which is a preferable aspect. In addition, the "total thickness" means the total thickness of all layers including the base material layer, the adhesive layer, and the antistatic layer of the laminate film.

The base material layer constituting the laminated film of the present invention is not particularly limited, but is preferably used for properties such as transparency, mechanical strength, thermal stability, moisture shielding properties, isotropy, flexibility, and dimensional stability. Excellent base material. In particular, since the base material has flexibility, the adhesive composition can be applied by a roll coater or the like, and it can be wound into a roll shape, which is useful.

What can be used as the aforementioned base material includes, for example, polyester-based polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate. ; Cellulose-based polymers such as cellulose diacetate, cellulose triacetate, etc.; Polycarbonate-based polymers; Acrylic-based polymers such as polymethyl methacrylate, etc. , typically a plastic film composed of a resin material that accounts for more than 50% by mass). Other examples of the aforementioned resin materials include styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers; polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, ethylene- Olefin-based polymers such as propylene copolymers; vinyl chloride-based polymers; and amide-based polymers such as nylon 6, nylon 6,6, and aromatic polyamides, etc., are used as resin materials. Other examples of the above-mentioned resin materials include imide-based polymers, silo-based polymers, polyether s-series polymers, polyether ether ketone-based polymers, polyphenylene sulfide-based polymers, and vinyl alcohol. type polymer, vinylidene chloride type polymer, vinyl butyral type polymer, arylate type polymer, polyoxymethylene type polymer, epoxy type polymer etc. The base material may also be a blend of two or more of the above-mentioned polymers.

As the aforementioned substrate, a plastic film composed of a transparent thermoplastic resin material can be preferably used. Among the aforementioned plastic films, a polyester film is used in a more preferable aspect. Here, the polyester film refers to a film having an ester bond with polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, etc. as its basic main skeleton. A polymer material (polyester resin) as the main resin component. Such polyester films have preferable properties such as being excellent in optical properties and dimensional stability on the substrate as a surface protective film.

Various additives such as antioxidants, ultraviolet absorbers, plasticizers, colorants (pigments, dyes, etc.), antistatic agents, and antiadhesives may be blended into the resin material constituting the aforementioned base material, if necessary. In addition, known or conventional surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, primer coating and the like can also be applied to the surface of the film used as the substrate.

The laminated film of the present invention may also have an antistatic layer on the base material layer, and as the aforementioned base material, a plastic film obtained by completing antistatic treatment can also be used. By using such a base material, the static electricity of the film itself is suppressed during peeling, which is preferable. In addition, the base material is a plastic film, and an antistatic treatment is applied to the plastic film, thereby reducing the static electricity of the laminated film itself, and can obtain an object with excellent antistatic ability to the adherend. Among them, the method for imparting an antistatic function is not particularly limited, and conventionally known methods can be used. Methods of conducting resin; methods of vapor deposition or plating of conductive substances; and methods of kneading antistatic agents, etc. When an antistatic agent is used, a glidant may be used together.

As a thickness of the said base material layer, it is 5-200 micrometers normally, Preferably it is about 10-100 micrometers. It is preferable that the thickness of the said base material layer is in the said range, since it is excellent in the workability|operativity of sticking to a to-be-adhered body and peeling workability from a to-be-adhered body.

On the laminated film of the present invention, if necessary, for the purpose of protecting the adhesive surface, a separator may be attached to the surface of the adhesive layer.

As the material constituting the spacer, there are paper and plastic film, and plastic film is suitably used in view of excellent surface smoothness. The film is not particularly limited as long as it can protect the film of the adhesive layer, and examples thereof include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, Vinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

The thickness of the spacer is usually 5 to 200 μm, preferably about 10 to 100 μm. It is preferable that it is in the said range, since the workability|operativity of sticking to an adhesive bond layer and peeling workability from an adhesive bond layer are excellent. The above-mentioned separator can also be subjected to release and antifouling treatment with polysiloxane-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agents, silica powder, etc., as required, coating type, kneading Antistatic treatment of type, vapor deposition type, etc.

The laminated film of the present invention can be suitably used as a surface protection film for optical members and the like. The laminated film of the present invention is also excellent in stability over time, and can be used for surface protection applications such as processing, transportation, and shipping, and thus can be used for surface protection of optical members such as polarizing plates. [Example]

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, the present invention is not limited to the following examples. In addition, unless otherwise specified, "part" and "%" in the following descriptions and tables represent solid content or active ingredient on the basis of mass.

In Examples and Comparative Examples, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) are measured in terms of polystyrene based on gel permeation chromatography (GPC). The measurement conditions of GPC are as follows.

[GPC measurement conditions] Measuring device: High-speed GPC device "HLC-8320GPC" manufactured by TOSOH Co., Ltd. Column: "TSK GUARDCOLUMN SuperHZ-L" made by TOSOH Co., Ltd. + "TSK gel SuperHZM-N" made by TOSOH Co., Ltd. + "TSK gel SuperHZM-N" made by TOSOH Co., Ltd. + "TSK gel SuperHZM-N made by TOSOH Co., Ltd." "＋TOSOH Co., Ltd. "TSK gel SuperHZM-N" Detector: RI (Differential Refractometer) Data processing: "EcoSEC Data Analysis Version 1.07" manufactured by TOSOH Co., Ltd. Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 0.35mL/min Measurement sample: 7.5 mg of the sample was dissolved in 10 ml of tetrahydrofuran, and the obtained solution was filtered through a microfilter as a measurement sample. Sample injection volume: 20μl Standard sample: According to the measurement manual of the aforementioned "HLC-8320GPC", the following monodisperse polystyrene known as the molecular weight was used.

(monodisperse polystyrene) "A-300" manufactured by Tosoh Co., Ltd. "A-500" manufactured by Tosoh Co., Ltd. "A-1000" manufactured by Tosoh Co., Ltd. "A-2500" manufactured by Tosoh Co., Ltd. "A-5000" manufactured by Tosoh Co., Ltd. "F-1" manufactured by Tosoh Co., Ltd. "F-2" manufactured by Tosoh Co., Ltd. "F-4" manufactured by Tosoh Co., Ltd. "F-10" manufactured by Tosoh Co., Ltd. "F-20" manufactured by Tosoh Co., Ltd. "F-40" manufactured by Tosoh Co., Ltd. "F-80" manufactured by Tosoh Co., Ltd. "F-128" manufactured by Tosoh Co., Ltd. "F-288" manufactured by Tosoh Co., Ltd.

(Synthesis example 1: Synthesis of perfluoropolyether compound) In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 20 g of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (a1-1-1) and 20 g were added as the second solvent Isopropyl ether, 0.02 g of p-methoxyphenol as a polymerization inhibitor, and 3.1 g of triethylamine as a neutralizing agent were added dropwise over 1 hour while starting stirring under air flow while maintaining the inside of the flask at 10°C. 2.7 g acryl chloride. After completion of the dropwise addition, the temperature was raised by stirring at 10°C for 1 hour, and after stirring at 30°C for 1 hour, the temperature was raised to 50°C and the reaction was performed by stirring for 10 hours. With respect to the obtained reaction liquid, it was confirmed by gas chromatography that acryl chloride disappeared.

(式中， 複數個X係各自獨立為全氟亞甲基或全氟伸乙基，每1分子中，全氟亞甲基平均存在7個、全氟伸乙基平均存在8個，氟原子的個數平均46。 根據GPC之數量平均分子量為1,500。)

(In the formula, a plurality of X series are each independently perfluoromethylene or perfluoroethylidene, and per molecule, there are 7 perfluoromethylene groups on average, 8 perfluoroethylene groups on average, and fluorine atoms. The number average is 46. The number average molecular weight according to GPC is 1,500.)

Next, 40 g of diisopropyl ether as a solvent and 80 g of ion-exchanged water were added to the reaction solution, and the mixture was stirred and left to stand, and the separated aqueous layer was removed and washed, and the procedure was repeated three times. To the washed reaction solution, 0.02 g of p-methoxyphenol as a polymerization inhibitor and 8 g of magnesium sulfate as a dehydrating agent were added, and the mixture was left to stand for 1 day for complete dehydration, and the dehydrating agent was filtered off. Next, the solvent was distilled off under reduced pressure to obtain a polymerizable compound having a poly(perfluoroalkylene ether) chain represented by the following formula (A1-1) (hereinafter abbreviated as "compound (A1-1)"). .) .

(式中， 複數個X係各自獨立為全氟亞甲基或全氟伸乙基，每1分子中，全氟亞甲基平均存在7個、全氟伸乙基平均存在8個，氟原子的個數平均46。)

(In the formula, a plurality of X series are each independently perfluoromethylene or perfluoroethylidene, and per molecule, there are 7 perfluoromethylene groups on average, 8 perfluoroethylene groups on average, and fluorine atoms. The average number is 46.)

In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 297.5 g of butyl acetate was added as a solvent, and the temperature was raised to 105° C. while stirring under a nitrogen stream. Next, 24.9 g of the above-mentioned compound (A1-1), 5.9 g of a monomethacrylate compound (number average molecular weight 5,000) having a polysiloxane bond represented by the following formula (A1-2), 6.2 g of an oxidative Ethyl-extended monoacrylate compound (BLEMMER AE-400, manufactured by NOF Corporation, the number of repetitions of oxidative ethyl-extended chains is about 10), 50.4 g of ethyl acrylate, 12.6 g of 4-hydroxybutyl acrylate, 133.3 g of butyl acetate as a solvent and 3.0 g of tert-Butylperoxy-2-ethylhexanoate as a radical polymerization initiator were prepared to prepare a mixed solution. The obtained mixed solution was added dropwise to the above glass flask at 105°C over 3 hours. After completion of the dropwise addition, the mixture was stirred at 105° C. for 5 hours, and then cooled to obtain a 30% by mass-containing solution of the perfluoropolyether compound (A1).

(前述式(A1-2)中，n ₂之數量平均為65。)

(In the aforementioned formula (A1-2), the number of n ₂ is 65 on average.)

As a result of analyzing the perfluoropolyether compound (A1) of the copolymer by GPC, the weight average molecular weight Mw was 5,300. Moreover, the content rate of fluorine in the reaction raw material used was 11 mass %.

(Synthesis Example 2: Synthesis of perfluoroalkyl-containing compound) 100 g of butyl acetate was added to the glass flask, and the temperature was raised to 95° C. in a nitrogen atmosphere over 30 minutes. Mix 24.9 g of 2-(perfluorohexyl)ethyl 2-(perfluorohexyl)ethyl acrylate, 5.9 g of the monomethacrylate compound having a polysiloxane bond represented by the aforementioned formula (A1-2), 6.2 g g Monoacrylate compound having oxidative ethyl extension chain represented by the following formula (A2-1), 50.4 g of ethyl acrylate, 12.6 g of 4-hydroxybutyl acrylate, 133.3 g of butyl acetate as a solvent, 3.0 g As a radical polymerization initiator, tertiary butyl peroxy-2-ethylhexanoate, a mixed solution was prepared. The obtained mixed solution was added dropwise to the above glass flask at 95°C over 3 hours. After completion of the dropwise addition, the mixture was stirred at 95°C for 3 hours, and then stirred at 110°C for 1.0 hour. Then, cooling was performed to obtain a 30% by mass solution of the perfluoroalkyl group-containing compound (A'1).

(前述式(A2-1)中，p之數量平均為10。)

(In the aforementioned formula (A2-1), the number of p is 10 on average.)

As a result of analyzing the perfluoroalkyl group-containing compound (A'1) of the copolymer by GPC, the weight average molecular weight Mw was 18,500.

Example 1 To the solid content of 100 parts of acrylic adhesive (CT-3088: manufactured by DIC Corporation), 2.9 parts of D-100K (manufactured by DIC Corporation) as a hardener (crosslinking agent) and 0.5 part of the obtained perfluoropolyether were added Compound (A1) was diluted with methyl ethyl ketone to a solid content of 35%, and thoroughly mixed to obtain an adhesive composition. The obtained adhesive composition was directly coated on the corona-treated surface of a polyester film having a thickness of 50 μm as a substrate using an automatic coating device bar coater (PI-1210: manufactured by TESTER CO,. LTD.) The thickness of the subsequent adhesive layer was 20 μm. Then, after drying at 85° C. for 3 minutes to form an adhesive layer, a 38 μm-thick polyester film separator coated with polysiloxane was coated on the adhesive layer to produce a laminated film. This laminated film was further aged at 40°C for 3 days, and was used as a sample for the evaluation test.

The following evaluations were performed on the obtained laminated film. The results are shown in Table 1. <Evaluation of initial adhesion> The obtained laminated film was put on a glass plate by one pass of pressure bonding with a 2 kgf roll, and it was set as an evaluation sample. After 24 hours of sticking, the adhesion and film peeling analyzer VPA-3 (manufactured by Kyowa Interface Science) was used to measure the adhesion of the evaluation sample. The measurement conditions are as follows. The adhesive force in two modes of the case where the stretching speed and the peeling speed were set to 150 mm/min and the case where the stretching speed and the peeling speed were set to 1,200 mm/min were evaluated. ・Drawing speed: 150mm/min, 1,200mm/min ・Peeling speed: 150mm/min, 1,200mm/min ・Peeling direction: 180° ・Sample size: 25mm×70mm

<Adhesion evaluation after 80℃×7 days> Separately, a sample for initial adhesion evaluation was produced, and the evaluation sample was stored at a temperature of 80°C for 7 days. Adhesion was evaluated on the evaluation sample after storage (after heat resistance test) in the same manner as in the evaluation of initial adhesion.

Comparative Example 1 A laminated film was produced and evaluated in the same manner as in Example 1, except that the perfluoroalkyl group-containing compound (A'1) was used instead of the perfluoropolyether compound (A1). The results are shown in Table 1.

Comparative Example 2 Except not adding the perfluoropolyether compound (A1), it carried out similarly to Example 1, produced the laminated film, and evaluated it. The results are shown in Table 1.

[Table 1] Example 1 Comparative Example 1 Comparative Example 2 Adhesion modifier Compound (A1) Compound (A'1) none Initial adhesion [N/25mm] Tensile speed・Peeling speed 150mm/min 0.05 0.06 0.11 Tensile speed and peeling speed 1200mm/min 0.19 0.25 0.39 Adhesion after heat resistance test [N/25mm] Tensile speed・Peeling speed 150mm/min 0.03 0.05 0.12 Tensile speed and peeling speed 1200mm/min 0.19 0.25 0.45

From the results in Table 1, it can be seen that the laminated film using the adhesive composition containing the perfluoropolyether compound (A1) is more effective than the adhesive composition containing the perfluoroalkyl group-containing compound (A'1). The laminated film (Comparative Example 1) and the laminated film (Comparative Example 2) using the adhesive composition containing no adhesive force modifier showed more excellent peeling properties. In addition, the perfluoroalkyl group-containing compound (A'1) is a compound having a perfluorohexyl group, so it is a compound of concern about environmental accumulation.

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Claims (11)

An adhesive composition comprising a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1) and an adhesive (B). The adhesive composition of claim 1, wherein the compound (A) has a polyoxyalkylene chain (a2) and/or a polysiloxane chain (a3). The adhesive composition of claim 1 or 2, wherein the compound (A) has a poly(perfluoroalkylene ether) chain (a1) on the main chain and a polyoxyalkylene chain (a2) on the side chain ) and/or polymers of polysiloxane chains (a3). The adhesive composition according to any one of claims 1 to 3, wherein the compound (A) is a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1), and is selected from the group consisting of polyoxyalkylene A copolymer in which one or more of the group consisting of the polymerizable monomer of the alkyl chain (a2) and the polymerizable monomer of the polysiloxane chain (a3) are used as a polymerization component. The adhesive composition of claim 4, wherein the polymerizable monomer system having a poly(perfluoroalkylene ether) chain (a1) has polymerizability at both ends of the poly(perfluoroalkylene ether) chain (a1) Unsaturated compounds. The adhesive composition according to any one of claims 1 to 5, wherein the compound (A) does not have a perfluoroalkyl group having 6 or more carbon atoms. The adhesive composition according to any one of claims 1 to 6, wherein the compound (A) does not have a fluorinated alkyl group. The adhesive composition according to any one of claims 1 to 7, wherein the content of the compound (A) is in the range of 0.01 to 20% by mass in the solid content of the adhesive composition. The adhesive composition according to any one of claims 1 to 8, wherein the adhesive (B) is an acrylic adhesive (b1) and/or a urethane adhesive (b2). A laminated film having an adhesive layer and a substrate layer of the adhesive composition according to any one of claims 1 to 9. The laminated film of claim 10 is a surface protection film of an optical member.