Adhesive composition and laminated film using the same

Abstract

Provided are an adhesive composition having excellent adhesive force adjustment effect, and a laminated film using the same as an adhesive layer and suitable for use as a surface protection film. Specifically, an adhesive composition comprising: a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1), and an adhesive (B).

Description

Technical Field

[0001] The present invention relates to an adhesive composition and a laminated film using the same. Background Art

[0002] Optical components such as polarizing plates, retardation plates, optical compensation films, and transparent conductive films used in liquid crystal displays, organic EL displays, and touch panels are attached with adhesive protective films to protect the surfaces during manufacturing, transportation, and use.

[0003] The protective film is a laminate composed of a transparent base material such as polyethylene, polyester, or polypropylene and an adhesive layer, and is peeled off from the adherend after fulfilling its purpose as a protective film.

[0004] When the protective film is peeled off from the adherend, it is required to be able to be peeled off cleanly with a small force and without leaving adhesive residue (residue) on the adherend surface.

[0005] In recent years, mechanical peeling of surface protection films has become the mainstream for optical members used in larger displays. The peeling speed often varies depending on the process, and protective films with better peelability and less adhesive residue are sought.

[0006] Surface protection films have been developed that satisfy the above requirements and have both slight adhesiveness that allows peeling with a small force and removability that allows clean repeeling even after temporary attachment (for example, Patent Document 1).

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2019-026707 Summary of the invention

[0010] Problem that the invention aims to solve

[0011] The surface protection film using the adhesive composition described in Patent Document 1 has a problem of insufficient peeling performance due to insufficient adhesive force adjustment effect of the adhesive composition. In addition, the adhesive composition described in Patent Document 1 contains a compound having a fluorinated alkyl group with 6 carbon atoms, which is a compound with worrying environmental accumulation.

[0012] The problem to be solved by the present invention is to provide a PSA composition having an excellent adhesive force adjustment effect, and a laminated film using the PSA composition in a PSA layer and being suitably used as a surface protection film.

[0013] Solutions for solving problems

[0014] The present inventors have conducted intensive studies and have found that a binder composition containing a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1) and a binder (B) can solve the above problems, thereby completing the present invention.

[0015] 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).

[0016] Effects of the Invention

[0017] According to the present invention, there can be provided a pressure-sensitive adhesive composition having an excellent pressure-sensitive adhesive force adjusting effect, and a laminated film using the pressure-sensitive adhesive composition in a pressure-sensitive adhesive layer and being preferably used as a surface protective film. DETAILED DESCRIPTION

[0018] Hereinafter, one embodiment of the present invention will be described. The present invention is not limited to the following embodiment, and can be implemented with appropriate additions and modifications within the scope of not impairing the effects of the present invention.

[0019] In addition, in this specification, "(meth)acrylate" means one or both of acrylate and methacrylate.

[0020] <Adhesive composition>

[0021] The adhesive composition of the present invention contains a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1) and an adhesive (B).

[0022] The perfluoropolyether compound (A) can function as an adhesive strength modifier, and by using the adhesive composition of the present invention, a laminated film having excellent peeling performance can be produced.

[0023] Hereinafter, each component contained in the adhesive composition of the present invention will be described.

[0024] [Perfluoropolyether compound (A)]

[0025] The perfluoropolyether compound (A) has a poly(perfluoroalkylene ether) chain (a1).

[0026] The poly(perfluoroalkylene ether) chain (a1) of the compound (A) may be a structure in which divalent fluorinated hydrocarbon groups and oxygen atoms are alternately linked, and examples thereof include groups represented by the following general formula (a1-1).

[0027]

[0028] (In the above formula (a1-1),

[0029] X is each independently a perfluoroalkylene group,

[0030] n1 is the number of repetitions. )

[0031] Among the plurality of Xs, two or more perfluoroalkylene groups may be present randomly or in blocks.

[0032] Examples of the perfluoroalkylene groups for X include the following perfluoroalkylene groups (X-1) to (X-6).

[0033]

[0034] The perfluoroalkylene group represented by X is preferably a perfluoroalkylene group having 1 to 3 carbon atoms, more preferably a perfluoromethylene group or a perfluoroethylene group, and further preferably a perfluoromethylene group and a perfluoroethylene group coexist in view of industrial availability.

[0035] When the perfluoromethylene group (X-1) and the perfluoroethylene group (X-2) coexist, the abundance ratio (X-1 / X-2) (ratio of the number) is preferably 1 / 10 to 10 / 1, more preferably 3 / 10 to 10 / 3.

[0036] The number of repetitions of n1 is, for example, an integer in the range of 1 to 300, preferably an integer in the range of 2 to 200, more preferably an integer in the range of 3 to 100, further preferably an integer in the range of 6 to 70, and most preferably an integer in the range of 12 to 50.

[0037] The number of fluorine atoms contained in one poly(perfluoroalkylene ether) chain (a1) is preferably in the range of 18 to 200 in total, more preferably in the range of 25 to 150 in total.

[0038] The content ratio of the poly(perfluoroalkylene ether) chain (a1) in 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 %.

[0039] The content ratio of the poly(perfluoroalkylene ether) chain (a1) can be calculated and adjusted based on the charged amount of the polymerizable monomer having the poly(perfluoroalkylene ether) chain (a1) described later.

[0040] The compound (A) preferably has a polyoxyalkylene chain (a2) and / or a silicone chain (a3). When the compound (A) has a polyoxyalkylene chain (a2) and / or a silicone chain (a3), the adhesive force adjusting function can be improved.

[0041] The polyoxyalkylene chain (a2) possessed by the compound (A) may be a plurality of alkylene chains having 1 to 6 carbon atoms, such as polyoxyethylene, polyoxypropylene, polyoxybutylene, etc., connected via ether bonds, and the structure of the alkylene chain may be either linear or branched.

[0042] Examples of the polyoxyalkylene chain (a2) contained in the compound (A) include a group represented by the following formula (a2-1).

[0043]

[0044] (In the above formula (a2-1),

[0045] Multiple R a2 are each independently an alkylene group having 1 to 6 carbon atoms,

[0046] n2 is the number of repetitions. )

[0047] Multiple R a2 In the above, two or more alkylene groups may be present randomly or in blocks.

[0048] The polyoxyalkylene chain (a2) is preferably a polyoxyethylene chain and / or a polyoxypropylene chain, and more preferably a polyoxyethylene chain.

[0049] When the polyoxyalkylene chain (a2) is composed of a polyoxyethylene chain and a polyoxypropylene chain, the polyoxyethylene chain and the polyoxypropylene chain in the polyoxyalkylene chain (a2) may be present randomly or in blocks.

[0050] The number of repetitions of n2 is, for example, an integer in the range of 1 to 200, preferably an integer in the range of 2 to 100, more preferably an integer in the range of 2 to 50, and further preferably an integer in the range of 3 to 50.

[0051] The content ratio of the polyoxyalkylene chain (a2) in 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 %.

[0052] The content ratio of the polyoxyalkylene chain (a2) can be calculated and adjusted based on the charge amount of the polymerizable monomer having the polyoxyalkylene chain (a2) described later.

[0053] Examples of the organosilicon chain (a3) ​​contained in the compound (A) include a group represented by the following formula (a3-1).

[0054]

[0055] (In the above formula (a3-1),

[0056] Multiple R a3 are each independently an alkyl group having 1 to 18 carbon atoms or a phenyl group,

[0057] n3 is the number of repetitions. )

[0058] R a3The alkyl group 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group and a hexadecyl group.

[0059] R a3 The alkyl group having 1 to 18 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.

[0060] The number of repetitions of n3 is, for example, an integer in the range of 1 to 200, and preferably an integer in the range of 1 to 150.

[0061] The content ratio of the silicone chain (a3) ​​in 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 %.

[0062] The content ratio of the silicone chain (a3) ​​can be calculated and adjusted based on the amount of the polymerizable monomer having the silicone chain (a3) ​​to be described later.

[0063] The compound (A) is preferably a copolymer containing, as polymerizable components, a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) and at least one selected from the group consisting of a polymerizable monomer having a polyoxyalkylene chain (a2) and a polymerizable monomer having a silicone chain (a3).

[0064] Here, the "polymerization components" refer to the components constituting the copolymer, and do not include the solvent, polymerization initiator, etc. that do not constitute the copolymer.

[0065] In the present invention, "polymerizable monomer" refers to a compound having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinyl ether, allyl, styryl, maleimide and other C=C-containing groups, preferably groups represented by the following formulas (U-1) to (U-6).

[0066]

[0067] The polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) is preferably a compound having polymerizable unsaturated groups at both ends of the poly(perfluoroalkylene ether) chain, and more preferably a compound having (meth)acryloyl groups or styryl groups at both ends of the poly(perfluoroalkylene ether) chain.

[0068] The molecular weight of the polymerizable monomer having the 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.

[0069] Specific examples of compounds having polymerizable unsaturated groups at both ends of the poly(perfluoroalkylene ether) chain include compounds represented by the following formulas (A1-1) to (A1-13). It should be noted that PFPE in formulas (A1-1) to (A1-13) is a linking group represented by the aforementioned formula (a1-1).

[0070]

[0071] 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.

[0072] Examples of methods for producing a compound having polymerizable unsaturated groups at both ends of a poly(perfluoroalkylene ether) chain include a method of obtaining a compound having one hydroxyl group at each end of a poly(perfluoroalkylene ether) chain by subjecting (meth)acrylic acid chloride to a dehydrochlorination reaction, a method of obtaining a compound by subjecting (meth)acrylic acid anhydride to a reaction, a method of obtaining a compound by subjecting (meth)acrylic acid to a dehydration reaction, a method of obtaining a compound by subjecting 2-(meth)acryloyloxyethyl isocyanate to a urethanization reaction, a method of obtaining a compound by subjecting itaconic anhydride to an esterification reaction, and a method of obtaining a compound by subjecting (meth)acrylic acid anhydride to a dehydration reaction. A method of obtaining the poly(perfluoroalkylene ether) by reacting a chloromethyl group-containing styrene with a base; a method of obtaining the poly(perfluoroalkylene ether) by esterifying a compound having one carboxyl group at each end of the poly(perfluoroalkylene ether) chain with 4-hydroxybutyl acrylate glycidyl ether; a method of obtaining the poly(perfluoroalkylene ether) by esterifying glycidyl (meth)acrylate; a method of introducing the poly(perfluoroalkylene ether) by reacting 2-hydroxyethyl (meth)acrylate with a compound having one isocyanate group at each end of the poly(perfluoroalkylene ether) chain; a method of obtaining the poly(perfluoroalkylene ether) by reacting 2-hydroxyethyl (meth)acrylamide.

[0073] Among them, the following are particularly preferred from the viewpoint of easy availability in synthesis: a method of obtaining a compound having one hydroxyl group at each end of a poly(perfluoroalkylene ether) chain by subjecting (meth)acrylic chloride to a dehydrochlorination reaction, a method of subjecting (meth)acrylic anhydride to a reaction, or a method of subjecting 2-(meth)acryloyloxyethyl isocyanate to a urethanization reaction.

[0074] 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).

[0075]

[0076] (In the above formulas (A2-1) and (A2-2),

[0077] R a21 , R a22 and Ra23 are each independently an alkylene group having 1 to 6 carbon atoms,

[0078] R a24 are each independently a hydrogen atom or a methyl group,

[0079] R a25 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

[0080] p, q and r are each independently an integer greater than 0, and p+q+r is an integer greater than 1.)

[0081] R a21 , R a22 and R a23 The alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 2 to 4 carbon atoms.

[0082] p+q+r is, for example, an integer in the range of 1 to 200, preferably an integer in the range of 2 to 100, more preferably an integer in the range of 2 to 50, and further preferably an integer in the range of 3 to 50.

[0083] 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.

[0084] As the polymerizable monomer having a polyoxyalkylene chain (a2), a commercially available product can be used. For example, hydroxy-terminated polyalkylene glycol mono(meth)acrylates include Blemmer PE-90, Blemmer PE-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 (all manufactured by NOF Corporation);As alkyl-terminated polyalkylene glycol mono(meth)acrylate, BlemmerPME-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 Co., Ltd.), LIGHT ESTER MC, LIGHT ESTER 130MA, LIGHT ESTER 041MA, Light Acrylate BO-A, Light Acrylate EC-A, Light Acrylate MTG-A, Light Acrylate 130A, Light Acrylate DPM-A, Light Acrylate P-200A, Light Acrylate NP-4EA, LightAcrylate NP-8EA (above, manufactured by Kyeisha Chemical Co., Ltd.), etc. ;

[0085] The polymerizable monomer having a polyoxyalkylene chain (a2) used as a polymerization component may be used alone or in combination of two or more.

[0086] The polymerizable monomer containing the silicone chain (a3) ​​is preferably a compound represented by the following formula (A3-1).

[0087]

[0088] (In the above formula (A3-1),

[0089] R a31 are each independently an alkyl group having 1 to 6 carbon atoms or -OSi(R a34 )3 represented by the group (R a34 are each independently an alkyl group having 1 to 3 carbon atoms),

[0090] R a32and R a33 are each independently an alkyl group having 1 to 6 carbon atoms,

[0091] R a35 is a hydrogen atom or a methyl group,

[0092] L 1 is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms,

[0093] n3 is the number of repetitions. )

[0094] R a31 , R a32 and R a34 Methyl is preferred.

[0095] R a33 Butyl is preferred.

[0096] The number of repetitions of n3 is in the range of, for example, 1 to 200, and preferably 1 to 150.

[0097] L 1 The alkylene group having 1 to 50 carbon atoms 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, an ethylene group, an n-propylene group or an isopropylene group.

[0098] L 1 The alkyleneoxy group having 1 to 50 carbon atoms is, for example, a group in which one -CH2- in the aforementioned alkylene group having 1 to 50 carbon atoms is substituted by -O-.

[0099] L 1 The alkyleneoxy group having 1 to 50 carbon atoms is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, further preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group or an octyleneoxy group.

[0100] L 1 The carbon atoms of the alkylene group having 1 to 50 carbon atoms and the alkyleneoxy group having 1 to 50 carbon atoms may be substituted with one or more substituents such as hydroxyl group, phenyl group, phenoxy group, etc.

[0101] As the polymerizable monomer containing the silicone chain (a3), compounds represented by the following formulae (A3-2) to (A3-9) are also preferred.

[0102]

[0103] (In the above formulas (A3-2) to (A3-9),

[0104] m is an integer of 1-6 for each independently.

[0105] n3 is a repetition number, and is in the range of 1 to 200, for example, and preferably in the range of 1 to 150.

[0106] R a32 Each is independently an alkyl group having 1 to 6 carbon atoms.

[0107] R a33 Each is independently an alkyl group having 1 to 6 carbon atoms.

[0108] R a35 are each independently a hydrogen atom or a methyl group.)

[0109] The molecular weight of the polymerizable monomer containing the silicone 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.

[0110] As the polymerizable monomer containing the silicone chain (a3), a commercially available item can be used.

[0111] The polymerizable monomer containing the silicone chain (a3) ​​used as a polymerization component may be used alone or in combination of two or more.

[0112] The compound (A) may use other polymerizable monomers than the polymerizable monomer having the poly(perfluoroalkylene ether) chain (a1), the polymerizable monomer having the polyoxyalkylene chain (a2) and the polymerizable monomer having the silicone chain (a3) ​​as the polymerizable component.

[0113] Examples of the other polymerizable monomer include a polymerizable monomer having an alkyl group (a4) having 1 to 18 carbon atoms and a polymerizable monomer having an aromatic group (a5) having 6 to 18 carbon atoms.

[0114] 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group and a hexadecyl group.

[0115] The alkyl group (a4) having 1 to 18 carbon atoms may be substituted with one or more substituents such as hydroxyl group, phenyl group, phenoxy group, etc.

[0116] 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.

[0117] Examples of the aromatic group (a5) having 6 to 18 carbon atoms include phenyl, naphthyl, anthracene-1-yl, phenanthrene-1-yl and the like.

[0118] The aromatic group (a5) having 6 to 18 carbon atoms may be further 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.

[0119] Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and a (meth)acryloyl group as the polymerizable unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate, alkyl esters having 1 to 18 carbon atoms of (meth)acrylate, such as ester, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, etc.; bridged cyclic alkyl esters having 1 to 18 carbon atoms of (meth)acrylate, such as dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, etc.

[0120] Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and a vinyl ether group as the polymerizable unsaturated group include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-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 and other alkyl vinyl ethers, cycloalkyl vinyl ethers, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl 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, 4-hydroxycyclohexyl vinyl ether, cyclohexane-1,4-dimethanol monovinyl ether and the like.

[0121] Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is an allyl group include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.

[0122] Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and a (meth)acrylamide group as the polymerizable unsaturated group include N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, and acryloylmorpholine.

[0123] Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and a maleimide group as the polymerizable unsaturated group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.

[0124] Examples of the polymerizable monomer having a hydroxyalkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate.

[0125] Examples of the polymerizable monomer having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms, in which the polymerizable unsaturated group is a (meth)acryloyl group, include benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

[0126] Examples of the polymerizable monomer having an aromatic group having 6 to 18 carbon atoms include styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0127] The above-mentioned other monomers used as the polymerization component may be used alone or in combination of two or more.

[0128] When compound (A) is a copolymer comprising a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) and a polymerizable monomer other than the polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) (a polymerizable monomer having a polyoxyalkylene chain (a2), a polymerizable monomer having a silicone chain (a3), and any other polymerizable monomer) as polymerization components, the polymerization form is not particularly limited.

[0129] The copolymer may be, for example, a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer or the like.

[0130] The charging ratio of each of the above-mentioned polymerizable monomers is not particularly limited.

[0131] The amount of the polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) is, for example, in the range of 1 to 90 mass %, preferably 1 to 80 mass %, more preferably 1 to 70 mass % of the total polymer components.

[0132] When compound (A) is a copolymer comprising, as polymerized components, a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) and at least one selected from the group consisting of a polymerizable monomer containing a polyoxyalkylene chain (a2) and a polymerizable monomer containing a silicone chain (a3), the total amount of the polymerizable monomer containing a polyoxyalkylene chain (a2) and the polymerizable monomer containing a silicone chain (a3) ​​is, for example, in the range of 5 to 2000 parts by mass, preferably in the range of 10 to 2000 parts by mass, and more preferably in the range of 15 to 2000 parts by mass, based on 100 parts by mass of the polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1).

[0133] The compound (A) is preferably a polymer containing a poly(perfluoroalkylene ether) chain (a1) in the main chain and a polyoxyalkylene chain (a2) and / or a silicone chain (a3) ​​in the side chain.

[0134] Here, the "main chain" refers to the longest molecular chain among the molecular chains constituting the compound (A), and the "side chain" refers to a molecular chain other than the main chain.

[0135] The compound (A) is preferably a copolymer comprising, as polymerizable components, a polymerizable monomer having polymerizable unsaturated groups at both ends of a poly(perfluoroalkylene ether) chain (a1) and at least one selected from the group consisting of a polymerizable monomer containing a polyoxyalkylene chain (a2) and a polymerizable monomer containing a silicone chain (a3).

[0136] It is preferred that the compound (A) does not have a perfluoroalkyl group having 6 or more carbon atoms.

[0137] The compound (A) does not contain a perfluoroalkyl group having 6 or more carbon atoms, thereby reducing environmental load.

[0138] It should be noted that the "perfluoroalkyl group having 6 or more carbon atoms" herein does not include a poly(perfluoroalkylene ether) chain.

[0139] The compound (A) preferably has no fluorinated alkyl group.

[0140] The compound (A) can ensure compatibility with the base resin by not having a fluorinated alkyl group.

[0141] The weight average molecular weight of compound (A) is not particularly limited, but is preferably in the range of 3,000 to 300,000, more preferably in the range of 3,000 to 200,000, from the viewpoint of compatibility with the adhesive (B) described later, ease of adjustment of adhesive strength, and reduction of residual adhesive, and is most preferably in the range of 4,000 to 100,000 from the viewpoint of uniformity of peeling force when used as a surface protection film for large-area optical components, etc.

[0142] The weight average molecular weight in the present invention is a value measured by the method described in Examples.

[0143] The method for producing the compound (A) is not particularly limited, and the compound (A) can be produced according to a known method.

[0144] Compound (A) can be produced by solution polymerization, bulk polymerization, emulsion polymerization, etc. based on polymerization mechanisms such as free radical polymerization, cationic polymerization, anionic polymerization, etc., and free radical polymerization is particularly convenient and industrially preferred. For example, it can be produced by adding a general free radical polymerization initiator to a polymerizable monomer mixture in an organic solvent to polymerize it.

[0145] Depending on the polymerizable monomer used, a dropping polymerization method in which polymerization is carried out while dropping the polymerizable monomer and the initiator into a reaction vessel is also effective for obtaining a copolymer having a uniform composition.

[0146] As the above-mentioned polymerization initiator, various substances can be used, for example, peroxides such as benzoyl peroxide and diacyl peroxide, azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, phenylazotriphenylmethane, metal chelates such as Mn(acac)3, transition metal catalysts that initiate living radical polymerization, etc.

[0147] If necessary, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, and octylthioglycolic acid, and thiol compounds having a coupling group such as γ-mercaptopropyltrimethoxysilane may be used as additives such as chain transfer agents.

[0148] The polymerization may be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent from the viewpoint of operability.

[0149] Examples of the solvent used in the polymerization include alcohols such as ethanol, isopropanol, n-butanol, isobutanol, and tert-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate; monocarboxylic acid esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, and butyl 2-oxopropionate; and dimethylformyl esters. Amines, dimethyl sulfoxide, polar solvents such as N-methylpyrrolidone, ethers such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and propylene glycol and esters thereof, halogen solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene and xylene, and fluorinated inert liquids such as perfluorooctane and perfluorotri-n-butylamine, etc.

[0150] These solvents may be used alone or in combination of two or more.

[0151] The solvent used for polymerization of the compound (A) can serve as the solvent of the adhesive composition of the present invention.

[0152] [Binder (B)]

[0153] As the adhesive (B), any adhesive having adhesive properties can be used without particular limitation, and examples thereof include acrylic adhesives, urethane adhesives, synthetic rubber adhesives, natural rubber adhesives, silicone adhesives, etc. Among these adhesives, acrylic adhesives (b1) and / or urethane adhesives (b2) are preferably used.

[0154] The (meth)acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) is obtained from raw material monomers containing a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms as a main component monomer.

[0155] The aforementioned (meth)acrylic acid monomers can be used as the main component in one or more kinds. By using the aforementioned (meth)acrylic acid monomers having an alkyl group with 1 to 14 carbon atoms, it becomes easy to control the adhesive force to the adherend (protected body) to be low, and a surface protection film with excellent easy peelability and re-peelability can be obtained.

[0156] It should be noted that the "main component" in the present invention refers to the largest component in the total amount of the constituent components, and the "main component" is preferably more than 40 mass %, more preferably more than 50 mass %, and even more preferably more than 60 mass %.

[0157] Examples of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-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, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, and n-tetradecyl (meth)acrylate.

[0158] Among the above-mentioned (meth)acrylic acid monomers, (meth)acrylic acid monomers having an alkyl group having 6 to 14 carbon atoms, such as 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, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, and n-tetradecyl (meth)acrylate, are preferred from the viewpoint of making it easy to control the adhesive strength to the adherend to be low and achieving excellent removability.

[0159] The (meth)acrylic acid-based polymer preferably contains 50% by mass or more of a (meth)acrylic acid-based monomer having an alkyl group having 1 to 14 carbon atoms, based on 100% by mass of the total amount of monomer components constituting the (meth)acrylic acid-based polymer, more preferably 60% by mass or more, further preferably 70 to 99% by mass, and most preferably 80 to 97% by mass.

[0160] The (meth)acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) preferably contains a (meth)acrylic monomer having a hydroxyl group as a raw material monomer. As the (meth)acrylic monomer having a hydroxyl group, one or more kinds may be used.

[0161] By using the (meth)acrylic monomer having a hydroxyl group, it becomes easy to control the crosslinking of the pressure-sensitive adhesive composition, and further, it becomes easy to control the balance between the improvement of wettability due to flow and the reduction of adhesive force during peeling, and it is also preferred from the viewpoint of antistatic.

[0162] Examples of the (meth)acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, and N-hydroxymethyl (meth)acrylamide. In particular, the use of a (meth)acrylic monomer having a hydroxyl group in which the number of carbon atoms of the alkyl group is 4 or more is preferred because it facilitates easy peeling during high-speed peeling.

[0163] The (meth)acrylic monomer having a hydroxyl group is preferably contained in an amount of 15 parts by mass or less, more preferably 1 to 13 parts by mass, further preferably 2 to 10 parts by mass, and most preferably 3 to 8 parts by mass, relative to 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms. If the amount is within the above range, it is easier to control the balance between the wettability of the adhesive composition and the cohesive force of the obtained adhesive layer, so it is preferred.

[0164] As other polymerizable monomer components, polymerizable monomers for adjusting the glass transition temperature and releasability of the (meth)acrylic polymer so that Tg is 0° C. or lower (usually -100° C. or higher) can be used to easily achieve a balance in adhesive performance.

[0165] As the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms and other polymerizable monomers other than the (meth)acrylic monomer having a hydroxyl group used in the (meth)acrylic polymer, a (meth)acrylic monomer having a carboxyl group may be used.

[0166] Examples of the (meth)acrylic monomer having a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate.

[0167] The amount of the (meth)acrylic monomer having a carboxyl group is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, further preferably less than 1 part by mass, further more preferably less than 0.2 parts by mass, and most preferably 0.01 parts by mass or more and less than 0.1 parts by mass, relative to 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms. If it is within the above range, it is preferred because it is possible to prevent the adhesive force from increasing over time (anti-adhesive force increase property).

[0168] In order to achieve both peel charging characteristics and adhesion-preventing properties, the (meth)acrylic monomer having a hydroxyl group and the (meth)acrylic monomer having a carboxyl group may be used in combination.

[0169] Furthermore, other polymerizable monomers other than the aforementioned (meth)acrylic monomers with an alkyl group having 1 to 14 carbon atoms, (meth)acrylic monomers with a hydroxyl group, and (meth)acrylic monomers with a carboxyl group used in the aforementioned (meth)acrylic polymer can be used without particular limitation. For example, components that improve cohesion / heat resistance such as cyano monomers, vinyl ester monomers, aromatic vinyl monomers, amide monomers, imide monomers, amino monomers, epoxy monomers, N-acryloyl morpholine, vinyl ether monomers, etc., which have functional groups that improve adhesion and act as crosslinking bases, can be appropriately used. Among them, nitrogen-containing monomers such as cyano monomers, amide monomers, imide monomers, amino monomers, and N-acryloyl morpholine are preferably used. By using nitrogen-containing monomers, it is possible to ensure a moderate adhesive force without floating, peeling, etc., and then a surface protection film with excellent shear force can be obtained, so it is useful. These polymerizable monomers can be used alone, and two or more can also be mixed and used.

[0170] Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

[0171] Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl laurate.

[0172] Examples of the aromatic vinyl monomer include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and other substituted styrenes.

[0173] Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinyl pyrrolidone, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide, N,N'-methylenebisacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, and diacetoneacrylamide.

[0174] Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.

[0175] Examples of the amino group-containing monomer include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate.

[0176] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and allyl glycidyl ether.

[0177] Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.

[0178] The amount of other polymerizable monomers other than 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 carboxyl group is preferably 0 to 40 parts by mass, based on 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, and is preferably 0 to 30 parts by mass from the viewpoint of being able to appropriately adjust good removability.

[0179] The (meth)acrylic polymer may further contain a polyoxyalkylene chain-containing reactive monomer as a monomer component.

[0180] The average c of the oxyalkylene units of the polyoxyalkylene-containing reactive monomer is preferably 1-40, more preferably 3-40, further preferably 4-35, particularly preferably 5-30.

[0181] When the average number of added moles is 1 or more, there is a tendency to efficiently obtain a pollution reduction effect on the adherend (protected body). In addition, when the average number of added moles is greater than 40, there is a tendency that the viscosity of the adhesive composition increases and coating becomes difficult. It should be noted that the end of the oxyalkylene chain may be a hydroxyl group as it is or may be substituted by other functional groups.

[0182] The polyoxyalkylene chain-containing reactive monomer may be used alone or in combination of two or more thereof, and its total content is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 4% by mass or less, particularly preferably 3% by mass or less, and even more preferably 1% by mass or less, based on the total amount of monomer components of the (meth)acrylic polymer.

[0183] Examples of the oxyalkylene unit of the reactive monomer containing a polyoxyalkylene chain include oxyalkylene units having an alkylene group having 1 to 6 carbon atoms, such as oxymethylene, oxyethylene, oxypropylene, oxybutylene, etc. The hydrocarbon group of the oxyalkylene chain may be linear or branched.

[0184] The reactive monomer containing a polyoxyalkylene chain is more preferably a reactive monomer having an ethylene oxide group. By using a (meth)acrylic polymer having a reactive monomer having an ethylene oxide group as the base polymer, the compatibility of the base polymer with the perfluoropolyether compound (A) is improved, and the bleeding to the adherend is appropriately suppressed, so that a low-staining adhesive composition is easily obtained.

[0185] Examples of the polyoxyalkylene chain-containing reactive monomer include (meth)acrylic acid alkylene oxide adducts and reactive surfactants having a reactive substituent such as an acryloyl group, a methacryloyl group, or an allyl group in the molecule.

[0186] Specific examples of the (meth)acrylic acid alkylene oxide adducts include polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polyethylene glycol-polybutylene glycol (meth)acrylate, polypropylene glycol-polybutylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, ethoxy polyethylene glycol (meth)acrylate, butoxy polyethylene glycol (meth)acrylate, octyloxy polyethylene glycol (meth)acrylate, lauryloxy polyethylene glycol (meth)acrylate, stearyloxy polyethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, octyloxy polyethylene glycol-polypropylene glycol (meth)acrylate, and the like.

[0187] Specific examples of the reactive surfactant include anionic reactive surfactants, nonionic reactive surfactants, and cationic reactive surfactants having a (meth)acryloyl group or an allyl group.

[0188] The (meth) acrylic polymer constituting the acrylic adhesive (b1) preferably has a weight average molecular weight (Mw) of 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 greater than 100,000, the cohesive force of the adhesive layer becomes appropriate, and there is a tendency to suppress residual adhesive. On the other hand, when the weight average molecular weight is less than 5,000,000, the fluidity of the polymer is appropriate, the wetting of the adherend becomes sufficient, and the bulging between the adherend and the adhesive layer of the surface protection film can be suppressed.

[0189] In addition, the said weight average molecular weight refers to the value measured by GPC (gel permeation chromatography).

[0190] The glass transition temperature (Tg) of the (meth)acrylic polymer constituting the acrylic adhesive (b1) is preferably 0°C or less, more preferably -10°C or less (usually -100°C or more). When the glass transition temperature is higher than 0°C, the polymer tends to be difficult to flow and wettability tends to be insufficient. In particular, by setting the glass transition temperature to -61°C or less, it is easy to obtain an adhesive layer with excellent wettability and easy peelability.

[0191] In addition, the glass transition temperature of a (meth)acrylic-type polymer can be adjusted to the said range by changing suitably the monomer component used and a composition ratio.

[0192] The polymerization method of the (meth)acrylic polymer is not particularly limited, and the polymerization can be carried out by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. In particular, solution polymerization is a more preferred method from the perspective of operability and low contamination to the adherend (protected body). In addition, the obtained polymer may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.

[0193] When a urethane adhesive (b2) is used as the adhesive (B), any appropriate urethane adhesive may be used. As the urethane adhesive (b2), preferably, a urethane adhesive comprising a urethane resin (urethane polymer) obtained by reacting a polyol with a polyisocyanate compound is used.

[0194] Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol.

[0195] Examples of the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate.

[0196] When a silicone adhesive is used in the adhesive layer, any appropriate silicone adhesive may be used. As such a silicone adhesive, a silicone adhesive obtained by blending or aggregating a silicone resin (silicone polymer, silicone component) may be preferably used.

[0197] In addition, examples of the silicone adhesive include addition reaction curing silicone adhesives and peroxide curing silicone adhesives. Among these silicone adhesives, addition reaction curing silicone adhesives are preferred because they do not use peroxides (benzoyl peroxide, etc.) and do not produce decomposition products.

[0198] As a curing reaction of the addition reaction curing type silicone adhesive, for example, when obtaining a polyalkyl silicone adhesive, a method of curing a polyalkyl hydrogen siloxane composition using a platinum catalyst is generally mentioned.

[0199] In the adhesive composition of the present invention, the mixing ratio of the perfluoropolyether compound (A) and the adhesive (B) can be appropriately set according to the desired adhesive force. When the adhesive composition of the present invention is used for the adhesive layer of the surface protection film, the content of the perfluoropolyether compound (A) is preferably 0.01 to 20% by mass, more preferably 0.1 to 5.0% by mass in the solid content of the adhesive composition. If it is within this range, the perfluoropolyether compound (A) can fully exert its function as an adhesive force regulator.

[0200] In addition, the "solid content" in the present invention refers to the content after removing the solvent from the adhesive composition.

[0201] [Other ingredients]

[0202] The adhesive composition of the present invention only needs to contain the perfluoropolyether compound (A) and the adhesive (B), and may contain other components such as various additives as long as the effects of the present invention are not impaired.

[0203] 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), by further containing a crosslinking agent, the structural unit, constituent ratio, selection and addition ratio of the aforementioned (meth)acrylic polymer can be appropriately adjusted and crosslinked, thereby making it easy to obtain an adhesive layer with better heat resistance.

[0204] As the crosslinking agent, isocyanate compounds, epoxy compounds, melamine resins, aziridine derivatives, and metal chelates can be used, and the use of isocyanate compounds is particularly preferred. In addition, these compounds can be used alone or in combination of two or more.

[0205] Examples of the isocyanate compound include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate (IPDI); aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, and xylene diisocyanate (XDI); and polyisocyanate modified products obtained by modifying these isocyanate compounds with an allophanate bond, a biuret bond, an isocyanurate bond, a uretdione bond, a urea bond, a carbodiimide bond, a uretonimine bond, an oxadiazinetrione bond, or the like.

[0206] Examples of commercially available isocyanate compounds include Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (all manufactured by Takeda Pharmaceutical Company Limited), Sumidur T80, Sumidur L, Desmodur N3400 (all manufactured by Sumitomo Bayer Urethane Co., Ltd.), Millionate MR, Millionate MT, CORONATE L, CORONATE HL, CORONATE HX (all manufactured by Nippon Polyurethane Industry Co., Ltd.), and the like.

[0207] These isocyanate compounds can be used alone, or two or more thereof can be mixed, or a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound can be used in combination. By mixing two or more crosslinking agents, both adhesion and resilience resistance (adhesion to curved surfaces) can be taken into account, and a laminated film with better adhesion reliability can be obtained.

[0208] Examples of the epoxy compound include N,N,N',N'-tetraglycidyl-m-xylylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.).

[0209] Examples of the melamine-based resin include hexamethylolmelamine and the like.

[0210] Examples of the aziridine derivatives include commercially available products under the trade names of HDU, TAZM, and TAZO (all manufactured by Souhto Pharmaceutical Industries, Ltd.).

[0211] Examples of the metal chelate include aluminum, iron, tin, titanium, nickel and the like as the metal component, and acetylene, methyl acetoacetate, ethyl lactate and the like as the chelate component.

[0212] The content of the crosslinking agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, further preferably 0.5 to 10 parts by mass, and most preferably 1.0 to 6 parts by mass, relative to 100 parts by mass of the (meth)acrylic polymer used in the acrylic adhesive (b1). By using the crosslinking agent within this range, the cohesive force of the obtained adhesive layer is appropriate, sufficient heat resistance is easily obtained, and residual adhesive is also suppressed.

[0213] The cross-linking agent may be used alone or in combination of two or more.

[0214] The pressure-sensitive adhesive composition may contain a cross-linking catalyst for more efficiently carrying out the above-mentioned arbitrary cross-linking reaction.

[0215] As the crosslinking catalyst, for example, tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris(acetylacetonate)iron, tris(hexane-2,4-dione)iron, tris(heptane-2,4-dione)iron, tris(heptane-3,5-dione)iron, tris(5-methylhexane-2,4-dione)iron, tris(octane-2,4-dione)iron, tris(6-methylheptane-2,4-dione)iron, tris(2,6-dimethylheptane-3,5-dione)iron, tris(nonane-2,4-dione)iron, tris(nonane-4,6-dione)iron, tris(2,2,6,6-tetramethylheptane-3,5-dione)iron, tris(tridecane-6,8-dione)iron, tris(1-phenyl)-2,4-dione)iron, tris(nonane-4,6-dione)iron, tris(2,2,6,6-tetramethylheptane-3,5-dione)iron, tris(tridecane-6,8-dione)iron, tris(1-phenyl)-2,4-dione)iron, tris(1-phenyl)-2,4-dione)iron, tris(2,6-dimethylheptane-3,5 ...2,6,6-tetra Iron catalysts such as tris(hexafluoroacetylacetonate)iron, tris(ethyl acetoacetate)iron, tris(n-propyl acetoacetate)iron, tris(isopropyl acetoacetate)iron, tris(n-butyl acetoacetate)iron, tris(sec-butyl acetoacetate)iron, tris(tert-butyl acetoacetate)iron, tris(methyl propionylacetate)iron, tris(ethyl propionylacetate)iron, tris(n-propyl propionylacetate)iron, tris(isopropyl propionylacetate)iron, tris(n-butyl propionylacetate)iron, tris(sec-butyl propionylacetate)iron, tris(tert-butyl propionylacetate)iron, tris(benzyl acetoacetate)iron, tris(dimethyl malonate)iron, tris(diethyl malonate)iron, trimethoxy iron, triethoxy iron, triisopropoxy iron, and ferric chloride may be used alone or in combination of two or more.

[0216] The content of the crosslinking catalyst is not particularly limited, and is preferably about 0.0001 to 1 part by mass, more preferably 0.001 to 0.5 parts by mass, relative to 100 parts by mass of the (meth)acrylic polymer. When the content is within the above range, the crosslinking reaction rate is fast when the adhesive layer is formed, and the pot life of the adhesive composition is also long, which is a preferred embodiment.

[0217] <Laminated film>

[0218] The laminated film of the present invention comprises an adhesive layer and a substrate layer, and the adhesive layer is a layer formed using the adhesive composition of the present invention.

[0219] The laminated film of the present invention can be manufactured by coating the adhesive composition of the present invention on at least one side of the substrate layer and crosslinking it. In addition, the laminated film of the present invention can also be manufactured by transferring the adhesive layer formed by crosslinking the adhesive composition of the present invention to at least one side of the substrate layer.

[0220] The method for forming the adhesive layer on the substrate layer is not particularly limited, and for example, the adhesive layer can be formed by coating the adhesive composition (solution) of the present invention on the substrate, and then drying and removing the polymerization solvent, etc. Thereafter, aging can be performed for the purpose of adjusting the migration of components of the adhesive layer, adjusting the crosslinking reaction, etc.

[0221] When the adhesive composition is applied to a substrate to produce a laminated film, one or more solvents other than the polymerization solvent may be newly added to the adhesive composition in order to uniformly apply the adhesive composition to the substrate.

[0222] As the formation method of the adhesive layer when manufacturing the laminated film of the present invention, the known method used in the manufacture of the adhesive tape can be used. Specifically, for example, roll coating, gravure coating, reverse roll coating, brush roll, spray coating, air knife coating, extrusion coating using a die coater, etc. can be mentioned.

[0223] The laminated film of the present invention is usually produced 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 a proper balance between removability and adhesiveness, which is preferred.

[0224] 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, adhesion, etc.), workability, and appearance properties are excellent, which is a preferred embodiment.

[0225] In addition, the "total thickness" refers to the total thickness of all layers including the base material layer, the adhesive layer, and the antistatic layer of the laminated film.

[0226] The substrate layer constituting the laminated film of the present invention is not particularly limited, but preferably uses a substrate having excellent properties such as transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, flexibility, dimensional stability, etc. It is particularly useful to make the substrate flexible so that the adhesive composition can be applied by a roll coater or the like and can be wound up in a roll.

[0227] Examples of the substrate that can be used include plastic films composed of resin materials having as main resin components (main components among the resin components, typically components accounting for 50% by mass or more) polyester polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate; cellulose polymers such as diacetate cellulose and triacetate cellulose; polycarbonate polymers; and acrylic polymers such as polymethyl methacrylate.

[0228] Other examples of the aforementioned resin materials include styrene polymers such as polystyrene and acrylonitrile-styrene copolymers; olefin polymers such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; vinyl chloride polymers; and amide polymers such as nylon 6, nylon 6,6, and aromatic polyamides.

[0229] Still other examples of the above-mentioned resin materials include imide polymers, sulfone polymers, polyethersulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, aromatic ester polymers, polyoxymethylene polymers, epoxy polymers, and the like.

[0230] The substrate may also be a mixture of two or more of the above polymers.

[0231] As the substrate, a plastic film formed of a transparent thermoplastic resin material can be preferably used. Among the plastic films, a polyester film is more preferably used. Here, the polyester film refers to a polymer material (polyester resin) having a main skeleton based on ester bonds, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate, as a main resin component. The polyester film has excellent optical properties and dimensional stability, and has preferred characteristics as a substrate for a surface protection film.

[0232] The resin material constituting the above-mentioned substrate may be mixed with various additives such as antioxidants, ultraviolet absorbers, plasticizers, colorants (pigments, dyes, etc.), antistatic agents, anti-blocking agents, etc. as needed. In addition, the surface of the film used as the substrate may be subjected to known or conventional surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of a primer.

[0233] The laminated film of the present invention may have an antistatic layer on the substrate layer, and a plastic film treated with antistatic treatment may be used as the substrate. By using such a substrate, the film itself is preferably prevented from being charged during peeling.

[0234] In addition, the substrate is a plastic film, and by subjecting the plastic film to an antistatic treatment, a plastic film having a reduced charge on the laminated film itself and excellent antistatic ability to the adherend can be obtained. It should be noted that there is no particular limitation on the method of imparting the antistatic function, and a conventionally known method can be used, such as a method of coating an antistatic resin containing an antistatic agent and a resin component, a conductive polymer, a conductive resin containing a conductive substance, a method of evaporating or plating a conductive substance, and a method of mixing an antistatic agent, etc. When an antistatic agent is used, a lubricant can also be used in combination.

[0235] The thickness of the substrate layer is usually 5 to 200 μm, preferably about 10 to 100 μm. When the thickness of the substrate layer is within the above range, the adhesion workability to the adherend and the peeling workability from the adherend are excellent, which is preferred.

[0236] In the laminated film of the present invention, a separator may be bonded to the surface of the adhesive layer for the purpose of protecting the adhesive surface, if necessary.

[0237] The material constituting the separator includes paper and plastic film, and plastic film can be preferably used from the aspect of excellent surface smoothness. The film is not particularly limited as long as it can protect the adhesive layer, and examples thereof include polyethylene film, polypropylene film, polybutylene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, and the like.

[0238] The thickness of the separator is usually 5 to 200 μm, preferably about 10 to 100 μm. When it is within the above range, the adhesion workability to the adhesive layer and the peeling workability from the adhesive layer are excellent, so it is preferred. If necessary, the separator can also be subjected to mold release and antifouling treatment based on silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agents, silica powder, etc., coating-type, mixing-type, vapor deposition-type and other antistatic treatments.

[0239] The laminated film of the present invention can be suitably used as a surface protection film for optical components, etc. The laminated film of the present invention is also excellent in stability over time and can be used for surface protection purposes during processing, transportation, and shipment, and is therefore useful for protecting the surface of optical components such as polarizing plates.

[0240] Example

[0241] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples.

[0242] In addition, "parts" and "%" in the following descriptions and tables are based on mass unless otherwise specified, and represent solid content or active ingredient.

[0243] In Examples and Comparative Examples, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

[0244] The measurement conditions of GPC are as follows.

[0245] [GPC measurement conditions]

[0246] Measuring device: High-speed GPC device "HLC-8320GPC" manufactured by Tosoh Corporation

[0247] Column: "TSK GUARDCOLUMN SuperHZ-L" manufactured by Tosoh Corporation + "TSK gelSuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gelSuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation

[0248] Detector: RI (differential refractometer)

[0249] Data processing: Tosoh Corporation "EcoSEC Data Analysis version 1.07"

[0250] Column temperature: 40°C

[0251] Developing solvent: tetrahydrofuran

[0252] Flow rate: 0.35mL / min

[0253] Measurement sample: 7.5 mg of a sample was dissolved in 10 ml of tetrahydrofuran, and the obtained solution was filtered with a microfilter to use as a measurement sample.

[0254] Sample injection volume: 20μl

[0255] Standard sample: According to the measurement manual of the aforementioned "HLC-8320GPC", the following monodisperse polystyrene having a known molecular weight was used.

[0256] (monodisperse polystyrene)

[0257] "A-300" manufactured by Tosoh Corporation

[0258] "A-500" manufactured by Tosoh Corporation

[0259] "A-1000" manufactured by Tosoh Co., Ltd.

[0260] "A-2500" manufactured by Tosoh Corporation

[0261] "A-5000" manufactured by Tosoh Corporation

[0262] "F-1" manufactured by Tosoh Corporation

[0263] "F-2" manufactured by Tosoh Corporation

[0264] "F-4" manufactured by Tosoh Corporation

[0265] "F-10" manufactured by Tosoh Corporation

[0266] "F-20" manufactured by Tosoh Corporation

[0267] "F-40" manufactured by Tosoh Corporation

[0268] "F-80" manufactured by Tosoh Corporation

[0269] "F-128" manufactured by Tosoh Corporation

[0270] "F-288" manufactured by Tosoh Corporation

[0271] (Synthesis Example 1: Synthesis of perfluoropolyether compound)

[0272] Into 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), 20 g of diisopropyl ether as a solvent, 0.02 g of p-methoxyphenol as an inhibitor and 3.1 g of triethylamine as a neutralizer were added, stirring was started under an air flow, and 2.7 g of acryloyl chloride was added dropwise over 1 hour while maintaining the temperature in the flask at 10°C.

[0273] After the dropwise addition was completed, the mixture was stirred at 10°C for 1 hour, the temperature was raised, and the mixture was stirred at 30°C for 1 hour, and the temperature was raised to 50°C and stirred for 10 hours to allow the reaction to proceed. The disappearance of acryloyl chloride was confirmed by gas chromatography of the obtained reaction liquid.

[0274]

[0275] (Where,

[0276] A plurality of Xs are each independently a perfluoromethylene group or a perfluoroethylene group. An average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present in one molecule, and an average of 46 fluorine atoms are present.

[0277] The number average molecular weight based on GPC was 1500. )

[0278] Next, 40 g of diisopropyl ether and 80 g of ion exchange water were added to the reaction solution as a solvent, stirred, and then allowed to stand, and the separated water layer was removed. This washing was repeated 3 times. 0.02 g of p-methoxyphenol was added to the reaction solution after washing as a polymerization inhibitor, and 8 g of magnesium sulfate was added as a dehydrating agent. The reaction solution was allowed to stand for 1 day to completely dehydrate, and the dehydrating agent was filtered out.

[0279] 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, simply referred to as “compound (A1-1)”).

[0280]

[0281] (Where,

[0282] A plurality of Xs are each independently a perfluoromethylene group or a perfluoroethylene group, and there are an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups in one molecule, and the average number of fluorine atoms is 46.)

[0283] In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 297.5 g of butyl acetate as a solvent was placed, and the temperature was raised to 105° C. while stirring under a nitrogen stream. Next, 24.9 g of the above compound (A1-1), 5.9 g of a monomethacrylate compound having a polysiloxane bond represented by the following formula (A1-2) (number average molecular weight 5000), 6.2 g of a monoacrylate compound having an ethylene oxide chain (Blemmer AE-400 manufactured by NOF Corporation, the number of repetitions of the ethylene oxide chain being 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-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator were mixed to prepare a mixed liquid.

[0284] The obtained mixed liquid was added dropwise to the glass flask over 3 hours at 105° C. After the addition was completed, the mixture was stirred at 105° C. for 5 hours and then cooled to obtain a solution containing 30% by mass of the perfluoropolyether compound (A1).

[0285]

[0286] (In the above formula (A1-2), the number of n2 is 65 on average.)

[0287] The perfluoropolyether compound (A1) as the copolymer was analyzed by GPC, and the weight average molecular weight Mw was 5300. The fluorine content in the reaction raw material used was 11% by mass.

[0288] (Synthesis Example 2: Synthesis of a perfluoroalkyl group-containing compound)

[0289] 100 g of butyl acetate was placed in a glass flask, and the temperature was raised to 95° C. over 30 minutes under a nitrogen atmosphere. 24.9 g of 2-(perfluorohexyl)ethyl acrylate, 5.9 g of the monomethacrylate compound having a polysiloxane bond represented by the above formula (A1-2), 6.2 g of the monoacrylate compound having an ethylene oxide 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, and 3.0 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator were mixed to prepare a mixed solution.

[0290] The obtained mixed solution was added dropwise to the glass flask at 95° C. over 3 hours. After the addition was completed, the mixture was stirred at 95° C. for 3 hours and then at 110° C. for 1.0 hour. Thereafter, the mixture was cooled to obtain a solution containing 30% by mass of the perfluoroalkyl group-containing compound (A′1).

[0291]

[0292] (In the above formula (A2-1), the number of p is 10 on average.)

[0293] The perfluoroalkyl group-containing compound (A'1) as a copolymer was analyzed by GPC, and the weight average molecular weight Mw was 18,500.

[0294] Example 1

[0295] To 100 parts of the solid content of an acrylic adhesive (CT-3088: manufactured by DIC Corporation), 2.9 parts of D-100K (manufactured by DIC Corporation) as a curing agent (crosslinking agent) and 0.5 parts of the obtained perfluoropolyether compound (A1) were added, and the mixture was diluted with methyl ethyl ketone so that the solid content became 35%, and mixed thoroughly to obtain an adhesive composition.

[0296] The obtained adhesive composition was directly applied to the corona-treated surface of a 50 μm thick polyester film as a substrate using an automatic coating device bar coater (PI-1210: manufactured by Tester) so that the thickness of the formed adhesive layer was 20 μm. After that, the adhesive layer was dried at 85°C for 3 minutes to form an adhesive layer, and then a 38 μm thick polyester film separator coated with silicone was covered on the adhesive layer to prepare a laminated film. The laminated film was then aged at 40°C for 3 days to prepare a sample for the evaluation test.

[0297] The obtained laminated film was subjected to the following evaluations. The results are shown in Table 1.

[0298] <Evaluation of initial adhesion>

[0299] The obtained laminated film was pressed and pasted on a glass plate by a 2kgf roller reciprocating once to prepare an evaluation sample. After 24 hours after pasting, the adhesion / film peeling analysis device VPA-3 (made by Kyowa Interface Science) was used to measure the adhesion of the evaluation sample. The measurement conditions are as follows. The adhesion was evaluated in two modes: the case where the tensile speed and the peeling speed were set to 150 mm / min, and the case where the tensile speed and the peeling speed were set to 1200 mm / min.

[0300] ·Stretching speed: 150mm / min, 1200mm / min

[0301] Peeling speed: 150mm / min, 1200mm / min

[0302] Peeling direction: 180°

[0303] Specimen size: 25mm×70mm

[0304] <Adhesion evaluation after 80°C x 7 days>

[0305] A sample used for the initial adhesive strength evaluation was prepared separately, and the evaluation sample was stored at a temperature of 80° C. for 7 days. The evaluation sample after storage (after the heat resistance test) was evaluated for adhesive strength in the same manner as in the initial adhesive strength evaluation.

[0306] Comparative Example 1

[0307] The results are shown in Table 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).

[0308] Comparative Example 2

[0309] The results are shown in Table 1.

[0310] [Table 1]

[0311]

[0312] From the results in Table 1, it can be seen that the laminated film using the adhesive composition containing the perfluoropolyether compound (A1) shows better peeling performance than the laminated film using the adhesive composition containing the perfluoroalkyl group-containing compound (A'1) (Comparative Example 1) and the laminated film using the adhesive composition not containing the adhesion regulator (Comparative Example 2).

[0313] The perfluoroalkyl group-containing compound (A'1) is a compound having a perfluorohexyl group and is therefore a compound that may cause concern for environmental accumulation.

Claims

1. An adhesive composition comprising: a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1), and an adhesive (B), The compound (A) is a copolymer comprising, as polymerizable components, a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) and at least one selected from the group consisting of a polymerizable monomer containing a polyoxyalkylene chain (a2) and a polymerizable monomer containing a silicone chain (a3), The poly(perfluoroalkylene ether) chain (a1) is a group represented by the general formula (a1-1): In the aforementioned formula (a1-1), X is each independently a perfluoroalkylene group, and n1 is the number of repetitions; The polyoxyalkylene chain (a2) is a group represented by formula (a2-1): In the above formula (a2-1), a plurality of R a2 Each is independently an alkylene group having 1 to 6 carbon atoms, and n2 is the number of repetitions; The organic silicon chain (a3) ​​is a group represented by formula (a3-1): In the above formula (a3-1), a plurality of R a3 Each is independently an alkyl group having 1 to 18 carbon atoms or a phenyl group, and n3 is the number of repetitions.

2. The adhesive composition according to claim 1, wherein The polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) is a compound having polymerizable unsaturated groups at both ends of the poly(perfluoroalkylene ether) chain (a1).

3. The adhesive composition according to claim 1, wherein The total amount of the polymerizable monomer containing the polyoxyalkylene chain (a2) and the polymerizable monomer containing the silicone chain (a3) ​​is in the range of 15 to 2000 parts by mass based on 100 parts by mass of the polymerizable monomer containing the poly(perfluoroalkylene ether) chain (a1).

4. The adhesive composition according to claim 2, wherein The total amount of the polymerizable monomer containing the polyoxyalkylene chain (a2) and the polymerizable monomer containing the silicone chain (a3) ​​is in the range of 15 to 2000 parts by mass based on 100 parts by mass of the polymerizable monomer containing the poly(perfluoroalkylene ether) chain (a1).

5. An adhesive composition comprising: a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1), and an adhesive (B), The compound (A) is a polymer having a poly(perfluoroalkylene ether) chain (a1) on the main chain and a polyoxyalkylene chain (a2) and / or an organosilicon chain (a3) ​​on the side chain. The poly(perfluoroalkylene ether) chain (a1) is a group represented by the general formula (a1-1): In the aforementioned formula (a1-1), X is each independently a perfluoroalkylene group, and n1 is the number of repetitions; The polyoxyalkylene chain (a2) is a group represented by formula (a2-1): In the above formula (a2-1), a plurality of R a2 Each is independently an alkylene group having 1 to 6 carbon atoms, and n2 is the number of repetitions; The organic silicon chain (a3) ​​is a group represented by formula (a3-1): In the above formula (a3-1), a plurality of R a3 Each is independently an alkyl group having 1 to 18 carbon atoms or a phenyl group, and n3 is the number of repetitions.

6. 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.

7. The adhesive composition according to any one of claims 1 to 5, wherein The compound (A) does not have a fluorinated alkyl group.

8. The adhesive composition according to any one of claims 1 to 5, 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.

9. The adhesive composition according to any one of claims 1 to 5, wherein The adhesive (B) is an acrylic adhesive (b1) and / or a urethane adhesive (b2). 10 . A laminated film comprising: an adhesive layer of the adhesive composition according to claim 1 , and a substrate layer. The laminated film according to claim 10 , which is a surface protection film for an optical member.

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