CN116323849A - Adhesive composition and laminated film using same - Google Patents

Abstract

Providing: an adhesive composition excellent in the effect of adjusting the adhesive force, and a laminated film which can be suitably used as a surface protective film when used for an adhesive layer. Specifically, an adhesive composition comprising: a perfluoropolyether compound (A) having a poly (perfluoroalkylene ether) chain (a 1), and a binder (B).

Description

Adhesive composition and laminated film using same

Technical Field

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

Background

An adhesive protective film is attached to the surface of an optical member such as a polarizing plate, a retardation plate, an optical compensation film, or a transparent conductive film used for a liquid crystal display, an organic EL display, a touch panel, or the like, to protect the surface during manufacturing, transportation, use, or the like.

The protective film is a laminate of a transparent base material such as polyethylene, polyester, polypropylene, or the like and an adhesive layer, and is peeled from an adherend after the purpose of the protective film is achieved.

When the protective film is peeled from the adherend, it is required to be able to peel cleanly with a small force, and no adhesive residue (adhesive residue) is generated on the surface of the adherend.

In recent years, in an optical member used for a large-sized display, peeling of a surface protective film by a machine has been a mainstream, and the peeling speed is often different depending on the process, and a protective film having more excellent peelability and less residual adhesive is demanded.

The following surface protective films were developed: in order to meet the above-described requirements, a surface protective film is provided which has both a micro-adhesiveness capable of peeling with a small force and a re-peelability capable of cleanly re-peeling even when temporarily attached (for example, patent document 1).

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open publication No. 2019-026707

Disclosure of Invention

Problems to be solved by the invention

The surface protective film using the adhesive composition described in patent document 1 has a problem of insufficient peeling performance because the adhesive force adjustment effect of the adhesive composition is insufficient. The pressure-sensitive adhesive composition described in patent document 1 contains a compound having a fluorinated alkyl group having 6 carbon atoms, which is a compound that has a concern about environmental accumulation.

The invention aims to provide: an adhesive composition excellent in the effect of adjusting the adhesive force, and a laminated film which can be suitably used as a surface protective film when used for an adhesive layer.

Solution for solving the problem

The present inventors have conducted intensive studies and as a result found that: the present invention has been accomplished in view of the above problems, and it is an object of the present invention to provide an adhesive composition comprising a perfluoropolyether compound (A) having a poly (perfluoroalkylene ether) chain (a 1) and an adhesive (B).

Namely, the present invention relates to an adhesive composition comprising: a perfluoropolyether compound (A) having a poly (perfluoroalkylene ether) chain (a 1), and a binder (B).

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there may be provided: an adhesive composition excellent in the effect of adjusting the adhesive force, and a laminated film which can be suitably used as a surface protective film when used for an adhesive layer.

Detailed Description

An embodiment of the present invention will be described below. The present invention is not limited to the following embodiments, and may be modified and implemented as appropriate within a range that does not impair the effects of the present invention.

In the present 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 (a 1), and a binder (B).

The perfluoropolyether compound (a) can function as an adhesion regulator, and by using the adhesive composition of the present invention, a laminated film excellent in peeling property can be produced.

The components contained in the adhesive composition of the present invention will be described below.

[ perfluoropolyether Compound (A) ]

The perfluoropolyether compound (A) has a poly (perfluoroalkylene ether) chain (a 1).

The poly (perfluoroalkylene ether) chain (a 1) of the compound (a) may have a structure in which 2-valent fluorinated hydrocarbon groups and oxygen atoms are alternately connected, and examples thereof include groups represented by the following general formula (a 1-1).

(in the above formula (a 1-1),

x is each independently a perfluoroalkylene group,

n1 is a repetition number. )

Of the plural X, 2 or more perfluoroalkylene groups may exist in a random or block form.

As the perfluoroalkylene group for 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 perfluoroethylene group, and if the perfluoroalkylene group is industrially easily available, it is more preferable that the perfluoromethylene group and the perfluoroethylene group coexist.

When the Quan Fu methylene group (X-1) and the perfluoroethylene group (X-2) coexist, the presence ratio (X-1/X-2) (the ratio of the numbers) is preferably 1/10 to 10/1, more preferably 3/10 to 10/3.

The repetition number 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, still more preferably an integer in the range of 6 to 70, and most preferably an integer in the range of 12 to 50.

The fluorine atoms contained in the poly (perfluoroalkylene ether) chain (a 1) 1 are preferably in the range of 18 to 200 in total, more preferably in the range of 25 to 150 in total.

The content of the poly (perfluoroalkylene ether) chain (a 1) 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 poly (perfluoroalkylene ether) chain (a 1) can be calculated and adjusted based on the amount of the polymerizable monomer having the poly (perfluoroalkylene ether) chain (a 1) to be described later.

The compound (A) preferably has a polyoxyalkylene chain (a 2) and/or a silicone chain (a 3). The compound (a) has a polyoxyalkylene chain (a 2) and/or a silicone chain (a 3), whereby the adhesion adjusting function can be improved.

The polyoxyalkylene chain (a 2) of the compound (a) may be, for example, a chain having 1 to 6 carbon atoms such as a polyoxyethylene, polyoxypropylene or polyoxybutylene chain, which is linked in plural by an ether bond, and may be a linear chain or a branched chain.

The polyoxyalkylene chain (a 2) of the compound (A) may be a group represented by the following formula (a 2-1).

(in the above formula (a 2-1),

multiple R' s ^a2 Each independently represents an alkylene group having 1 to 6 carbon atoms,

n2 is a repetition number. )

Multiple R' s ^a2 More than 2 kinds of alkylene groups may be present in a random or block form.

The polyoxyalkylene chain (a 2) is preferably a polyoxyethylene chain and/or a polyoxypropylene chain, more preferably a polyoxyethylene chain.

When the polyoxyalkylene chain (a 2) is formed of a polyoxyethylene chain and a polyoxypropylene chain, the polyoxyethylene chain and the polyoxypropylene chain in the polyoxyalkylene chain (a 2) may be present randomly or in a block form.

The repetition number 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 still more preferably an integer in the range of 3 to 50.

The content of the polyoxyalkylene chain (a 2) 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 (a 2) can be calculated and adjusted based on the amount of the polymerizable monomer having the polyoxyalkylene chain (a 2) to be added, which will be described later.

The silicone chain (a 3) of the compound (A) may be a group represented by the following formula (a 3-1).

(in the above formula (a 3-1),

multiple R' s ^a3 Each independently represents an alkyl group having 1 to 18 carbon atoms or a phenyl group,

n3 is a repetition number. )

R ^a3 The 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, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a n-hexyl group, a cyclohexyl group, a n-octyl group, a hexadecyl group and the like.

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

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

The content of the silicone chain (a 3) 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 silicone chain (a 3) can be calculated and adjusted based on the amount of the polymerizable monomer having the silicone chain (a 3) to be described later.

The compound (a) is preferably a copolymer containing, as a polymerization component, a polymerizable monomer having a poly (perfluoroalkylene ether) chain (a 1) and 1 or more selected from the group consisting of a polymerizable monomer having a polyoxyalkylene chain (a 2) and a polymerizable monomer having a silicone chain (a 3).

The "polymerization component" herein means a component constituting the copolymer, and does not include a solvent, a polymerization initiator, and the like which do not constitute the copolymer.

In the present invention, the "polymerizable monomer" refers to a compound having a polymerizable unsaturated group, and examples of the polymerizable unsaturated group include a group containing c=c such as a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acrylamido group, a vinyl ether group, an allyl group, a styryl group, and a maleimide group, and groups represented by the following formulas (U-1) to (U-6) are preferable.

The polymerizable monomer having the poly (perfluoroalkylene ether) chain (a 1) 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.

The molecular weight of the polymerizable monomer having the poly (perfluoroalkylene ether) chain (a 1) is, for example, in the range of 300 to 50000, preferably in the range of 300 to 30000, more preferably in the range of 300 to 10000.

Specific examples of the compound 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). The PFPE of the formulae (A1-1) to (A1-13) is a linking group represented by the formula (A1-1).

The polymerizable monomer having the poly (perfluoroalkylene ether) chain (a 1) used as the polymerization component may be used alone or in combination of 1 or more than 2 kinds.

Examples of the method for producing a compound having polymerizable unsaturated groups at both ends of a poly (perfluoroalkylene ether) chain include the following methods: a method comprising a step of subjecting a compound having 1 hydroxyl group at each of both ends of a poly (perfluoroalkylene ether) chain to a desalting reaction, a step of subjecting (meth) acrylic anhydride to a dehydrating reaction, a step of subjecting 2- (meth) acryloyloxyethyl isocyanate to a urethanization reaction, a step of subjecting itaconic anhydride to an esterification reaction, and a step of reacting in the presence of a chloromethyl-containing styrene and a base; a method comprising esterifying 4-hydroxybutyl acrylate glycidyl ether with a compound having 1 carboxyl group at each of both ends of a poly (perfluoroalkylene ether) chain, or a method comprising esterifying glycidyl (meth) acrylate; a method of introducing 2-hydroxyethyl (meth) acrylate into a compound having 1 isocyanate group at each of both ends of a poly (perfluoroalkylene ether) chain, and a method of reacting 2-hydroxyethyl (meth) acrylamide.

Among them, in terms of being readily available synthetically, particular preference is given to: a method in which a compound having 1 hydroxyl group at each of both ends of a poly (perfluoroalkylene ether) chain is subjected to a desalting reaction, a method in which (meth) acrylic anhydride is reacted, or a method in which 2- (meth) acryloyloxyethyl isocyanate is subjected 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).

(in the aforementioned formulae (A2-1) and (A2-2),

R ^a21 、R ^a22 and R is ^a23 Each independently represents an alkylene group having 1 to 6 carbon atoms,

R ^a24 each independently is 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 integers of 0 or more, and p+q+r is an integer of 1 or more. )

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

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 still more preferably an integer in the range of 3 to 50.

The molecular weight of the polymerizable monomer having the polyoxyalkylene chain (a 2) is, for example, in the range of 50 to 20000, preferably in the range of 50 to 10000, more preferably in the range of 50 to 800.

The polymerizable monomer having the polyoxyalkylene chain (a 2) may be commercially available ones, and examples thereof include: as hydroxyl-terminated polyalkylene glycol mono (meth) acrylates, 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, blemmer30PET-800, blemmer 55PET-800, blemmer AET series, blemmer30 PPT-800, blemmer 50PPT-800, blemmer 70PPT-800, blemmer APT series, blemmer10PPB-500B, blemmer APB-500B (above, manufactured by Niday oil Co., ltd.); as alkyl terminal polyalkylene glycol mono (meth) acrylates, blemmer PME-100, blemmer PME-200, blemmer PME-400, blemmer PME-1000, blemmer PME-4000, blemmer AME-400, blemmer 50POEP-800B, blemmer AOEP-800B, blemmer PLE-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 Nikko corporation), LIGHT ESTER MC, LIGHT ESTER MA, 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, light Acrylate NP-8EA (manufactured by co-grong corporation, above), and the like.

The polymerizable monomer having a polyoxyalkylene chain (a 2) used as the polymerization component may be used alone in an amount of 1 or in an amount of 2 or more.

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

(in the above formula (A3-1),

R ^a31 each independently is an alkyl group having 1 to 6 carbon atoms or-OSi (R) ^a34 ) ₃ The radicals (R ^a34 Each independently is an alkyl group having 1 to 3 carbon atoms),

R ^a32 and R is ^a33 Each independently represents an alkyl group having 1 to 6 carbon atoms,

R ^a35 is a hydrogen atom or a methyl group,

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

n3 is a repetition number. )

R ^a31 、R ^a32 And R is ^a34 Methyl is preferred.

R ^a33 Butyl is preferred.

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

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, and still more preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group.

L ¹ An alkylene oxide group having 1 to 50 carbon atoms is, for example, 1-CH in the alkylene group having 1 to 50 carbon atoms ₂ -a group substituted by-O-.

L ¹ The alkylene oxide group having 1 to 50 carbon atoms is preferably an alkylene oxide group having 1 to 15 carbon atoms, more preferably an alkylene oxide group having 1 to 8 carbon atoms, and still more preferably a methylene oxide group, an ethylene oxide group, a propylene oxide group, an oxytrimethylene group, a butylene oxide group Oxy-tetramethylene, pentyleneoxy, heptyleneoxy or octyleneoxy.

Respectively form L ¹ The carbon atoms of the alkylene group having 1 to 50 carbon atoms and the alkylene oxide group having 1 to 50 carbon atoms are optionally substituted with 1 or more substituents such as a hydroxyl group, a phenyl group, a phenoxy group, etc.

As the polymerizable monomer containing the silicone chain (A3), compounds represented by the following formulas (A3-2) to (A3-9) are also preferable.

(in the above formulae (A3-2) to (A3-9),

m is each independently an integer of 1 to 6.

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

R ^a32 Each independently represents an alkyl group having 1 to 6 carbon atoms.

R ^a33 Each independently represents an alkyl group having 1 to 6 carbon atoms.

R ^a35 Each independently is a hydrogen atom or a methyl group. )

The molecular weight of the polymerizable monomer containing the silicone chain (a 3) is, for example, in the range of 400 to 30000, preferably in the range of 400 to 20000, more preferably in the range of 400 to 15000.

As the polymerizable monomer containing the silicone chain (a 3), commercially available ones can be used.

The polymerizable monomer containing the silicone chain (a 3) used as the polymerization component may be used alone in 1 kind or in combination of 2 or more kinds.

The compound (a) may use a polymerizable monomer other than the polymerizable monomer having the poly (perfluoroalkylene ether) chain (a 1), the polymerizable monomer having the polyoxyalkylene chain (a 2), and the polymerizable monomer having the silicone chain (a 3) for the polymerizable component.

Examples of the other polymerizable monomer include a polymerizable monomer having an alkyl group (a 4) having 1 to 18 carbon atoms, and a polymerizable monomer having an aromatic group (a 5) having 6 to 18 carbon atoms.

The alkyl group (a 4) 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, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a n-hexyl group, a cyclohexyl group, a n-octyl group, a hexadecyl group and the like.

The alkyl group (a 4) having 1 to 18 carbon atoms may be substituted with 1 or more substituents such as a hydroxyl group, a phenyl group, and a phenoxy group.

The alkyl group (a 4) 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 (a 5) having 6 to 18 carbon atoms include phenyl, naphthyl, anthracene-1-yl, phenanthren-1-yl and the like.

The aromatic group (a 5) having 6 to 18 carbon atoms may be further substituted with a substituent such as a hydroxyl group, an alkyl group, an alkoxy group, or the like, for example, a phenyl group containing 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 a polymerizable unsaturated group being a (meth) acryloyl group include alkyl esters having 1 to 18 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate; and bridged cyclic alkyl esters having 1 to 18 carbon atoms of (meth) acrylic acid such as dicyclopentadienyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like.

Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and having a vinyl ether group as a polymerizable unsaturated group include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, alkyl vinyl ethers such as cyclohexyl vinyl ether, cycloalkyl vinyl ether, 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-hydroxy-2-methylpropyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexane-1, 4-dimethanol monovinyl ether, and the like.

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

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

Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and a maleimide group as a polymerizable unsaturated group include methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, and cyclohexyl maleimide.

Examples of the polymerizable monomer having a hydroxyalkyl group having 1 to 18 carbon atoms and a (meth) acryloyl group as the polymerizable unsaturated 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.

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 and a (meth) acryloyl group as the polymerizable unsaturated group include benzyl (meth) acrylate, 2-phenoxymethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

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

The other monomers used as the polymerization component may be used alone or in combination of 1 or more than 2.

In the case where the compound (a) is a copolymer containing, as a polymerization component, a polymerizable monomer having a poly (perfluoroalkylene ether) chain (a 1) and a polymerizable monomer other than the polymerizable monomer having a poly (perfluoroalkylene ether) chain (a 1) (a polymerizable monomer having a polyoxyalkylene chain (a 2), a polymerizable monomer having a silicone chain (a 3), and any other polymerizable monomer), the polymerization form is not particularly limited.

The copolymer may be, for example, any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.

The ratio of the polymerizable monomers to be added is not particularly limited.

The amount of the polymerizable monomer having the poly (perfluoroalkylene ether) chain (a 1) is, for example, in the range of 1 to 90% by mass, preferably in the range of 1 to 80% by mass, more preferably in the range of 1 to 70% by mass, of the entire polymerization component.

In the case of the compound (a) being a copolymer containing, as a polymerization component, 1 or more kinds of polymerizable monomers having the poly (perfluoroalkylene ether) chain (a 1) and polymerizable monomers selected from the group consisting of the polymerizable monomers having the polyoxyalkylene chain (a 2) and the polymerizable monomers having the silicone chain (a 3), the total amount of the polymerizable monomers having the polyoxyalkylene chain (a 2) and the polymerizable monomers having the silicone chain (a 3) 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, relative to 100 parts by mass of the polymerizable monomers having the poly (perfluoroalkylene ether) chain (a 1).

The compound (a) is preferably a polymer containing a poly (perfluoroalkylene ether) chain (a 1) in the main chain, and a polyoxyalkylene chain (a 2) and/or a silicone chain (a 3) in the side chain.

The "main chain" herein means the longest molecular chain among the molecular chains constituting the compound (A), and the "side chain" means a molecular chain other than the main chain.

The compound (a) is preferably a copolymer containing, as a polymerization component, a polymerizable monomer having polymerizable unsaturated groups at both ends of the poly (perfluoroalkylene ether) chain (a 1), and 1 or more kinds selected from the group consisting of a polymerizable monomer containing the polyoxyalkylene chain (a 2) and a polymerizable monomer containing the silicone chain (a 3).

The compound (a) preferably does not have a perfluoroalkyl group having 6 or more carbon atoms.

The compound (A) can reduce the environmental load by eliminating the perfluoroalkyl group having 6 or more carbon atoms.

Here, "perfluoroalkyl group having 6 or more carbon atoms" does not contain a poly (perfluoroalkylene ether) chain.

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

The compound (a) has no fluorinated alkyl group, and thus can ensure compatibility with the base resin.

The weight average molecular weight of the compound (a) is not particularly limited, but is preferably in the range of 3000 to 300000, more preferably in the range of 3000 to 200000, and most preferably in the range of 4000 to 100000 from the viewpoint of uniformity of peeling force when used as a surface protective film for a large-area optical member or the like, from the viewpoints of compatibility with the adhesive (B) to be described later, ease of adjustment of the adhesive force, reduction of residual glue, and the like.

The weight average molecular weight in the present invention is a value measured according to the method described in examples.

The method for producing the compound (a) is not particularly limited, and 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 or the like based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method or an anionic polymerization method, and particularly, a radical polymerization method is simple and industrially preferred. For example, the polymer composition can be produced by adding a general radical polymerization initiator to an organic solvent to polymerize the polymerizable monomer mixture.

Depending on the polymerizable monomer used, a dropping polymerization method in which a polymer monomer and an initiator are added dropwise to a reaction vessel while polymerizing is also effective for obtaining a copolymer having a uniform composition.

As the polymerization initiator, various kinds of substances can be used, and examples thereof include peroxides such as benzoyl peroxide and diacyl peroxide, azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate and phenylazotriphenylmethane, and Mn (acac) ₃ Metal chelates, transition metal catalysts for initiating living radical polymerization, and the like.

If necessary, a thiol compound having a coupling group such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, octyl thioglycolic acid and the like can be used as an additive such as a chain transfer agent.

The polymerization may be carried out in the presence or absence of a solvent, and from the viewpoint of operability, it is preferably carried out in the presence of a solvent.

As the solvent used in the polymerization, examples thereof include alcohols such as ethanol, isopropanol, N-butanol, isobutanol, and t-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, butyl 2-oxopropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate, dimethylformamide, dimethylsulfoxide, and polar solvents such as N-methylpyrrolidone, ethers such as methyl cellosolve, butyl carbitol, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, halogen solvents such as 1, 1-trichloroethane and trichloromethane, ethers such as tetrahydrofuran and dioxane, aromatic compounds such as benzene, toluene and xylene, and fluorinated inert liquids such as perfluorooctane and perfluoro tri-N-butylamine.

These solvents may be used alone or in combination of 1 or more than 2.

The solvent used in the polymerization of the compound (a) may be used as the solvent of the adhesive composition of the present invention.

[ adhesive (B) ]

The adhesive (B) may be used without particular limitation, and examples thereof include an acrylic adhesive, a urethane adhesive, a synthetic rubber adhesive, a natural rubber adhesive, and a silicone adhesive. Among these adhesives, the acrylic adhesive (b 1) and/or the urethane adhesive (b 2) are preferably used.

The (meth) acrylic polymer constituting the acrylic adhesive (b 1) is obtained from a raw material monomer comprising a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms as a main component monomer.

The (meth) acrylic monomer may be used in an amount of 1 or 2 or more. By using the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the adhesion to an adherend (protected body) can be easily controlled to be low, and a surface protective film excellent in light peelability and re-peelability can be obtained.

In the present invention, the "main component" means the largest component among the total amount of constituent components, and the "main component" is preferably more than 40 mass%, more preferably more than 50 mass%, and still more preferably more than 60 mass%.

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, t-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.

Among the (meth) acrylic monomers, from the viewpoint of easily controlling the adhesion to an adherend to be low and improving the removability, preferred is a (meth) acrylic monomer 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, n-tetradecyl (meth) acrylate.

The (meth) acrylic monomer containing an alkyl group having 1 to 14 carbon atoms is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70 to 99% by mass, and most preferably 80 to 97% by mass based on 100% by mass of the total amount of monomer components constituting the (meth) acrylic polymer.

The (meth) acrylic polymer constituting the acrylic adhesive (b 1) preferably contains a (meth) acrylic monomer having a hydroxyl group as a raw material monomer. As the (meth) acrylic monomer having a hydroxyl group, 1 or 2 or more kinds may be used.

By using the (meth) acrylic monomer having a hydroxyl group, it is possible to easily control the crosslinking and the like of the adhesive composition, and further to easily control the balance between the improvement of wettability by flow and the reduction of adhesion during peeling, and it is also preferable from the viewpoint of antistatic.

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 (meth) methyl acrylate, and N-methylol (meth) acrylamide. Particularly, when a (meth) acrylic monomer having a hydroxyl group having 4 or more carbon atoms as an alkyl group is used, light peeling at high-speed peeling is facilitated, and is preferable.

The hydroxyl group-containing (meth) acrylic monomer is preferably contained in an amount of 15 parts by mass or less, more preferably 1 to 13 parts by mass, still more preferably 2 to 10 parts by mass, and most preferably 3 to 8 parts by mass, based on 100 parts by mass of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms. If the content falls within the above range, it becomes easy to control the balance between the wettability of the adhesive composition and the cohesive force of the resulting adhesive layer, and therefore it is preferable.

As the other polymerizable monomer component, a polymerizable monomer for adjusting the glass transition temperature and releasability of the (meth) acrylic polymer may be used so that Tg is 0 ℃ or lower (usually-100 ℃ or higher) for the reason that the balance of adhesive properties is easily obtained.

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.

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

The (meth) acrylic monomer having a carboxyl group is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably less than 1 part by mass, still more preferably less than 0.2 part by mass, most preferably 0.01 part by mass or more and less than 0.1 part by mass, based on 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, the adhesive force can be prevented from increasing with time (the adhesion-preventing property increases), which is preferable.

For the purpose of achieving both of the peeling electrification characteristic and the adhesion force rising property, the (meth) acrylic monomer having a hydroxyl group and the (meth) acrylic monomer having a carboxyl group may be used in combination.

Further, the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the (meth) acrylic monomer having a hydroxyl group, and other polymerizable monomers other than the (meth) acrylic monomer having a carboxyl group used in the (meth) acrylic polymer may be used without particular limitation. For example, a component having a functional group that functions as a crosslinking group and functions as a crosslinking group, such as a cyano group-containing monomer, a vinyl ester monomer, an aromatic vinyl monomer, an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, an N-acryloylmorpholine, and a vinyl ether monomer, can be suitably used. Among them, nitrogen-containing monomers such as cyano group-containing monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, and N-acryloylmorpholine are preferably used. The use of the nitrogen-containing monomer is useful because it can ensure moderate adhesion such as no lifting or peeling, and can provide a surface protective film excellent in shear force. These polymerizable monomers may be used alone or in combination of two or more.

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

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

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

Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N-dimethylacrylamide, N, N-diethylacrylamide, N' -methylenebisacrylamide, N-dimethylaminopropyl acrylamide, N-dimethylaminopropyl methacrylamide, diacetone acrylamide and the like.

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

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

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

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

The amount of the polymerizable monomer 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 from the viewpoint of suitably adjusting good re-peelability, it is preferably 0 to 30 parts by mass.

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

The average c of the oxyalkylene units of the polyoxyalkylene group-containing reactive monomer is preferably 1 to 40, more preferably 3 to 40, still more preferably 4 to 35, particularly preferably 5 to 30.

When the average addition mole number is 1 or more, the contamination reducing effect of the adherend (protected object) tends to be obtained efficiently. In addition, when the average addition mole number is more than 40, the viscosity of the adhesive composition tends to increase, and coating tends to be difficult. The terminal of the oxyalkylene chain may be a hydroxyl group, or may be substituted with another functional group or the like.

The polyoxyalkylene chain-containing reactive monomer may be used alone or in combination of 2 or more, and the total content of the monomer components of the (meth) acrylic polymer is preferably 20 mass% or less, 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, and still more preferably 1 mass% or less.

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

The polyoxyalkylene chain-containing reactive monomer described above 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 a base polymer, the compatibility of the base polymer with the perfluoropolyether compound (a) is improved, and bleeding to an adherend is suitably suppressed, so that a low-pollution adhesive composition can be easily obtained.

Examples of the polyoxyalkylene chain-containing reactive monomer include (meth) acrylic acid alkylene oxide adducts, and reactive surfactants having reactive substituents such as acryl, methacryl, and allyl groups in the molecule.

Specific examples of the alkylene oxide (meth) acrylate adducts include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol (meth) acrylate, lauryloxypolyethylene glycol (meth) acrylate, stearyloxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol (meth) acrylate, and the like.

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

The weight average molecular weight (Mw) of the (meth) acrylic polymer constituting the acrylic adhesive (b 1) is preferably 10 to 500 tens of thousands, more preferably 20 to 200 tens of thousands, still more preferably 30 to 80 tens of thousands. When the weight average molecular weight is more than 10 ten thousand, the cohesive force of the adhesive layer becomes appropriate, and the residual adhesive tends to be suppressed. On the other hand, when the weight average molecular weight is 500 ten thousand or less, the fluidity of the polymer is appropriate, and the wetting of the adherend becomes sufficient, so that the occurrence of swelling between the adherend and the pressure-sensitive adhesive layer of the surface protective film can be suppressed.

The weight average molecular weight refers to a value measured by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the (meth) acrylic polymer constituting the acrylic adhesive (b 1) is preferably 0℃or lower, more preferably-10℃or lower (usually-100℃or higher). When the glass transition temperature is higher than 0 ℃, the polymer tends to be less likely to flow and insufficient in wetting. In particular, when the glass transition temperature is-61℃or lower, an adhesive layer excellent in wettability and light releasability can be easily obtained.

The glass transition temperature of the (meth) acrylic polymer can be adjusted to the above range by appropriately changing the monomer components and the composition ratio to be used.

The polymerization method of the (meth) acrylic polymer is not particularly limited, and polymerization may be carried out by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc., and in particular, solution polymerization is a more preferable method from the viewpoint of handling properties, low contamination property to an adherend (protected body), etc. The polymer obtained may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or the like.

When the urethane-based adhesive (B2) is used as the adhesive (B), any suitable urethane-based adhesive may be used. As the urethane-based adhesive (b 2), a urethane-based adhesive containing a urethane resin (urethane-based polymer) obtained by reacting a polyol with a polyisocyanate compound is preferable.

Examples of the polyol include polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.

Examples of the polyisocyanate compound include diphenylmethane diisocyanate, toluene diisocyanate, and hexamethylene diisocyanate.

When the silicone adhesive is used for the adhesive layer, any suitable silicone adhesive may be used. As such a silicone-based adhesive, a silicone-based adhesive obtained by blending or aggregating silicone resins (silicone-based polymer, silicone component) can be preferably used.

The silicone-based adhesive may be an addition reaction curable silicone-based adhesive or a peroxide curable silicone-based adhesive. Among these silicone adhesives, addition reaction curable silicone adhesives are preferred in that no peroxide (benzoyl peroxide or the like) is used and no decomposition products are generated.

As the curing reaction of the addition reaction curable silicone-based adhesive, for example, when a polyalkyl silicone-based adhesive is obtained, a method of curing a polyalkyl hydrosiloxane composition using a platinum catalyst is generally mentioned.

In the adhesive composition of the present invention, the blending ratio of the perfluoropolyether compound (a) to the adhesive (B) may be appropriately set according to the desired adhesive force. When the adhesive composition of the present invention is used for the adhesive layer of a surface protective 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, based on the solid content of the adhesive composition. If the amount is within this range, the perfluoropolyether compound (A) can sufficiently function as an adhesion regulator.

In the present invention, the term "solid component" means a component obtained by removing a solvent from an adhesive composition.

[ other Components ]

The adhesive composition of the present invention may contain other components such as various additives as long as the effects of the present invention are not impaired, as long as the adhesive composition contains the perfluoropolyether compound (a) and the adhesive (B).

The adhesive composition of the present invention preferably contains a crosslinking agent as the other component. For example, in the case where the adhesive composition of the present invention contains the (meth) acrylic polymer as the adhesive (B), the crosslinking agent is further contained, whereby the structural unit, the composition ratio, the selection and the addition ratio of the crosslinking agent, and the like of the (meth) acrylic polymer are appropriately adjusted and crosslinked, and thereby an adhesive layer having more excellent heat resistance can be easily obtained.

As the crosslinking agent, isocyanate compounds, epoxy compounds, melamine resins, aziridine derivatives, metal chelates, and the like can be used, and particularly, the use of isocyanate compounds is preferable. These compounds may be used alone or in combination of 2 or more.

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, isophorone diisocyanate (IPDI), aromatic isocyanates such as 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate, and Xylene Diisocyanate (XDI), and polyisocyanate modified products obtained by modifying these isocyanate compounds with allophanate bond, biuret bond, isocyanurate bond, uretdione bond, urea bond, carbodiimide bond, uretonimine bond, and oxadiazinetrione bond.

Examples of the commercial products of the isocyanate compounds include those having trade names of Takenate 300S, takenate, takenate 600, takenate D165N, takenate D178N (manufactured by Wuta Kogyo Co., ltd.), sumidur T80, sumidur L, desmodur N3400 (manufactured by Sumitomo Bayer Urethane Co. Ltd.), milliconate MR, milliconate MT, COROnate L, COROnate HL, CORONTX (manufactured by Nippon Polyurethane Industry Co. Ltd.).

These isocyanate compounds may be used alone, or 2 or more may be used in combination, or a 2-functional isocyanate compound and a 3-functional or more isocyanate compound may be used in combination. By using 2 or more kinds of crosslinking agents in combination, both the adhesiveness and the rebound resilience (adhesiveness to a curved surface) can be achieved, and a laminated film having more excellent 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-diglycidyl aminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi gas chemical Co., ltd.), and the like.

Examples of the melamine resin include hexamethylol melamine.

Examples of the aziridine derivative include commercially available products such as trade name HDU, TAZM, TAZO (manufactured by the above-mentioned chemical company, inc.).

Examples of the metal chelate include aluminum, iron, tin, titanium, and nickel, and examples of the chelate include acetylene, methyl acetoacetate, and ethyl lactate.

The content of the crosslinking agent is, for example, preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, still more preferably 0.5 to 10 parts by mass, and most preferably 1.0 to 6 parts by mass, based on 100 parts by mass of the (meth) acrylic polymer used in the acrylic adhesive (b 1). When the crosslinking agent is used in this range, the cohesive force of the obtained adhesive layer is appropriate, sufficient heat resistance is easily obtained, and the residual adhesive is suppressed.

The crosslinking agent may be used alone in an amount of 1 kind, or may be used in an amount of 2 or more kinds.

The adhesive composition may contain a crosslinking catalyst for more effectively performing any of the above crosslinking reactions.

As the above-mentioned crosslinking catalyst, a catalyst, tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, etc., tris (acetylacetonate) iron, tris (hexane-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, 6-tetramethylheptane-3, 5-dione) iron tris (tridecane-6, 8-dione) iron, tris (1-phenylbutane-1, 3-dione) iron, tris (hexafluoroacetylacetonate) iron, tris (ethylacetoacetate) iron, tris (n-propyl acetoacetate) iron, tris (isopropyl acetoacetate) iron, tris (n-butyl acetoacetate) iron, tris (sec-butyl acetoacetate) iron, tris (t-butyl acetoacetate) iron, tris (methyl propionylacetate) iron, tris (ethylacetoacetate) iron, tris (n-propyl propionylacetate) iron, tris (isopropyl propionylacetate) iron, tris (n-butyl propionylacetate) iron, iron-based catalysts such as iron tris (sec-butyl propionylacetate), iron tris (tert-butyl propionylacetate), iron tris (benzyl acetoacetate), iron tris (dimethyl malonate), iron tris (diethyl malonate), trimethoxyiron, triethoxy iron, triisopropoxy iron, and ferric chloride. These crosslinking catalysts may be used in an amount of 1 or 2 or more.

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 part by mass, based on 100 parts by mass of the (meth) acrylic polymer. In the case of the above range, the crosslinking reaction is rapid in forming the adhesive layer, and the pot life of the adhesive composition is long, which is a preferable mode.

< laminated film >)

The laminated film of the present invention has an adhesive layer and a base layer, and the adhesive layer is a layer formed using the adhesive composition of the present invention.

The laminated film of the present invention can be produced by coating the adhesive composition of the present invention on at least one side of a base layer and crosslinking it. The laminated film of the present invention can be produced by transferring an adhesive layer obtained by previously crosslinking the adhesive composition of the present invention onto at least one surface of a base layer.

The method for forming the adhesive layer on the substrate layer is not particularly limited, and for example, the adhesive composition (solution) of the present invention is applied to a substrate, and the adhesive layer is formed on the substrate by drying and removing a polymerization solvent or the like. Thereafter, curing for the purpose of controlling the migration of components of the adhesive layer, controlling the crosslinking reaction, and the like may be performed.

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 so that the adhesive composition can be uniformly applied to the substrate.

As a method for forming the pressure-sensitive adhesive layer in the production of the laminated film of the present invention, a known method used in the production of pressure-sensitive adhesive tapes can be used. Specifically, examples thereof include roll coating, gravure coating, reverse roll coating, brush roll, spray coating, air knife coating, extrusion coating using a die coater, and the like.

The laminated film of the present invention is usually produced such that the thickness of the pressure-sensitive adhesive layer is about 1 to 200. Mu.m, preferably about 3 to 100. Mu.m. When the thickness of the pressure-sensitive adhesive layer is within this range, a suitable balance between re-peelability and adhesiveness is easily obtained, and thus it is preferable.

The total thickness of the laminated film of the present invention is preferably 1 to 400. Mu.m, more preferably 10 to 200. Mu.m, most preferably 20 to 150. Mu.m. When the total thickness of the laminated film is within this range, the adhesive properties (re-peelability, adhesiveness, etc.), handling properties, and appearance properties are excellent, and a preferable mode is obtained.

The "total thickness" refers to the total thickness of all layers including the base layer, the adhesive layer, and the antistatic layer of the laminated film.

The substrate layer constituting the laminated film of the present invention is not particularly limited, and a substrate excellent in characteristics such as transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, flexibility, and dimensional stability is preferably used. In particular, it is useful to impart flexibility to a substrate, so that the adhesive composition can be applied by a roll coater or the like, and can be wound into a roll.

Examples of the substrate that can be used include polyester polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate; cellulose polymers such as diacetylcellulose and triacetylcellulose; a polycarbonate-based polymer; a plastic film comprising a resin material containing an acrylic polymer such as polymethyl methacrylate as a main resin component (a component constituting 50 mass% or more of the main resin component).

As other examples of the resin material, styrene polymers such as polystyrene and acrylonitrile-styrene copolymer; olefin polymers such as polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, and ethylene-propylene copolymer; vinyl chloride-based polymers; nylon 6, and amide polymers such as aromatic polyamides are resin materials.

As still another example of the resin material, imide-based polymer, sulfone-based polymer, polyether ether ketone-based polymer, polyphenylene sulfide-based polymer, vinyl alcohol-based polymer, vinylidene chloride-based polymer, vinyl butyral-based polymer, aryl ester-based polymer, polyoxymethylene-based polymer, epoxy-based polymer, and the like can be given.

A substrate comprising a mixture of 2 or more of the above polymers is also possible.

As the base material, a plastic film formed of a transparent thermoplastic resin material can be preferably used. Among the plastic films, a polyester film is more preferable. Here, the polyester film is a film comprising a polymer material (polyester resin) having a main skeleton based on an ester bond, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate, as a main resin component. The polyester film is excellent in optical characteristics, dimensional stability, and the like, and has preferable characteristics as a base material of the surface protective film.

The resin material constituting the base material may be blended with various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a colorant (pigment, dye, etc.), an antistatic agent, and an antiblocking agent, if necessary. The surface of the film used as the substrate may be subjected to a known or conventional surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of primer.

The laminated film of the present invention may have an antistatic layer on a base material layer, and as the base material, a plastic film subjected to antistatic treatment may be used. By using such a base material, the electrification of the film itself at the time of peeling is suppressed, which is preferable.

The base material is a plastic film, and the antistatic treatment is performed on the plastic film, so that a plastic film having reduced electrification of the laminated film itself and excellent antistatic ability to an adherend can be obtained. The method for imparting an antistatic function is not particularly limited, and conventionally known methods may be used, and examples thereof include: 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 vapor deposition or plating a conductive substance, a method of kneading an antistatic agent, and the like. When an antistatic agent is used, a lubricant may be used in combination.

The thickness of the base layer is usually 5 to 200. Mu.m, preferably about 10 to 100. Mu.m. When the thickness of the base material layer is within the above range, the adhesion to an adherend and the release from the adherend are excellent, and therefore, are preferable.

In the laminated film of the present invention, a separator may be bonded to the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface, if necessary.

As a material constituting the separator, there are paper and a plastic film, and from the viewpoint of excellent surface smoothness, a plastic film can be suitably used. The film is not particularly limited as long as it can protect the pressure-sensitive 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, and ethylene-vinyl acetate copolymer film.

The thickness of the separator is usually 5 to 200. Mu.m, preferably about 10 to 100. Mu.m. When the amount is within the above range, the adhesion to the pressure-sensitive adhesive layer and the peeling from the pressure-sensitive adhesive layer are excellent, and therefore, the pressure-sensitive adhesive layer is preferable. The separator may be subjected to a release agent based on silicone, fluorine, long-chain alkyl or fatty acid amide, a release treatment such as silica powder, an anti-fouling treatment, an antistatic treatment such as a coating, kneading, or vapor deposition, as required.

The laminated film of the present invention can be suitably used as a surface protective film for optical members and the like. The laminated film of the present invention is also excellent in stability with time and can be used for surface protection purposes such as processing, transportation, and shipping, and is therefore useful for protecting the surface of an optical member such as a polarizing plate.

Examples

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples.

The present invention is not limited to the following examples. The "parts" and "%" in the following description and tables represent solid components or active components, unless otherwise specified.

In examples and comparative examples, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values obtained by converting polystyrene based on Gel Permeation Chromatography (GPC).

The measurement conditions of GPC are as follows.

[ GPC measurement conditions ]

Measurement device: HLC-8320GPC apparatus of Tosoh Co., ltd "

Column: "TSK GUARDCOLUMN SuperHZ-L" manufactured by Tosoh Co., ltd. "TSK gel SuperHZM-N" manufactured by Tosoh Co., ltd. "TSK" manufactured by Tosoh Co., ltd. ";" TSK gel SuperHZM-N "manufactured by Tosoh Co., ltd." +TSK gel SuperHZM-N "manufactured by Tosoh Co., ltd.", TSK gel SuperHZM-N "

A detector: RI (differential refractometer)

And (3) data processing: dongsoh Co., ltd. "EcoSEC Data Analysis version 1.07.07"

Column temperature: 40 DEG C

Developing solvent: tetrahydrofuran (THF)

Flow rate: 0.35 mL/min

Measuring a sample: 7.5mg of the sample was dissolved in 10ml of tetrahydrofuran, and the obtained solution was filtered by a microfilter to obtain a measurement sample.

Sample injection amount: 20 μl of

Standard sample: according to the measurement manual of "HLC-8320GPC", the following monodisperse polystyrene having a known 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

20g of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (a 1-1-1), 20g of diisopropyl ether as a solvent, 0.02g of p-methoxyphenol as a polymerization inhibitor, and 3.1g of triethylamine as a neutralizing agent were charged into a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, and 2.7g of acryloyl chloride was added dropwise over 1 hour while maintaining the inside of the flask at 10℃under stirring under an air flow.

After the completion of the dropwise addition, the mixture was stirred at 10℃for 1 hour, heated, stirred at 30℃for 1 hour, heated to 50℃and stirred for 10 hours, whereby the reaction was carried out. The disappearance of the acryloyl chloride was confirmed by gas chromatography measurement on the obtained reaction solution.

/>

(in the formula (I),

each of the plurality of X's is independently a perfluoromethylene group or a perfluoroethylene group, and the number of fluorine atoms is 46 on average for an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups present in each 1 molecule.

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

Subsequently, 40g of diisopropyl ether and 80g of ion-exchanged water were added to the reaction solution, followed by stirring and standing, the separated aqueous layer was removed, and the washing was repeated 3 times. To the reaction solution after washing, 0.02g of p-methoxyphenol as a polymerization inhibitor was added, 8g of magnesium sulfate as a dehydrating agent was added, and the mixture was left standing for 1 day to completely dehydrate, and the dehydrating agent was filtered off.

Next, the solvent is distilled off under reduced pressure, whereby a polymerizable compound having a poly (perfluoroalkylene ether) chain represented by the following formula (A1-1) (hereinafter, abbreviated as "compound (A1-1)") is obtained.

(in the formula (I),

each of the plurality of X's is independently a perfluoromethylene group or a perfluoroethylene group, and the number of fluorine atoms is 46 on average for an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups present in each 1 molecule. )

To a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 297.5g of butyl acetate as a solvent was charged, and the mixture was stirred under a nitrogen flow and heated to 105 ℃. Next, 24.9g of the above-mentioned compound (A1-1), 5.9g of a monomethacrylate compound having a polysiloxane bond represented by the following formula (A1-2) (number average molecular weight 5000), 6.2g of a monoacrylate compound having an ethylene oxide chain (manufactured by Nikko Co., ltd., blemmer AE-400, repetition number of the ethylene oxide chain of about 10), 50.4g of ethyl acrylate, 12.6g of 4-hydroxybutyl acrylate, 133.3g of butyl acetate as a solvent, and 3.0g of t-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator were mixed to prepare a mixed solution.

The obtained mixture was added dropwise to the glass flask at 105℃over 3 hours. After completion of the dropwise addition, the mixture was stirred at 105℃for 5 hours and then cooled to obtain a 30 mass% solution containing the perfluoropolyether compound (A1).

(in the above formula (A1-2), n ₂ Is 65. )

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

Synthesis example 2 Synthesis of perfluoroalkyl group-containing Compound

Into a glass flask, 100g of butyl acetate was charged, and the temperature was raised to 95℃over 30 minutes under a nitrogen atmosphere. A mixture was prepared by mixing 24.9g of 2- (perfluorohexyl) ethyl acrylate, 5.9g of a monomethacrylate compound having a polysiloxane bond represented by the above formula (A1-2), 6.2g of a monoacrylate compound having an ethylene oxide chain represented by the following formula (A2-1), 50.4g of ethyl acrylate, 12.6g of 4-hydroxybutyl acrylate, 133.3g of butyl acetate as a solvent, and 3.0g of t-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator.

The obtained mixture was added dropwise to the glass flask at 95℃over 3 hours. After the completion of the dropwise addition, the mixture was stirred at 95℃for 3 hours and then at 110℃for 1.0 hour. Thereafter, the mixture was cooled to obtain a 30 mass% solution containing the perfluoroalkyl group-containing compound (A' 1).

(in the above formula (A2-1), the number average of p is 10.)

As a result of analysis of the perfluoroalkyl group-containing compound (A' 1) as a copolymer by GPC, the weight average molecular weight Mw was 18500.

Example 1

2.9 parts of D-100K (DIC Co., ltd.) as a curing agent (crosslinking agent) and 0.5 part of the obtained perfluoropolyether compound (A1) were added to 100 parts of the solid content of the acrylic pressure-sensitive adhesive (CT-3088: DIC Co., ltd.) and diluted with methyl ethyl ketone so that the solid content became 35%, followed by thorough mixing, to obtain a pressure-sensitive adhesive composition.

The adhesive composition obtained was directly applied to the corona-treated surface of a polyester film having a thickness of 50 μm as a substrate, using an automatic applicator bar coater (PI-1210: manufactured by Tester Co., ltd.) so that the thickness of the adhesive layer after formation became 20. Mu.m. After drying at 85℃for 3 minutes to form an adhesive layer, the adhesive layer was covered with a 38 μm thick polyester film separator coated with silicone to prepare a laminated film. The laminated film was further cured at 40℃for 3 days to prepare a sample for evaluation test.

The obtained laminated film was evaluated as follows. The results are shown in Table 1.

< evaluation of initial adhesion >

The obtained laminated film was bonded to a glass plate by pressing with a 2kgf roller 1 time back and forth, and an evaluation sample was prepared. After 24 hours from the adhesion, the adhesion of the sample was measured and evaluated using an adhesion/film-coating peeling analyzer VPA-3 (manufactured by the department of interfacial science). The measurement conditions are as follows. The adhesive force was evaluated in two modes, i.e., 150 mm/min for the stretching speed and the peeling speed and 1200 mm/min for the stretching speed and the peeling speed.

Drawing speed: 150 mm/min, 1200 mm/min

Peeling speed: 150 mm/min, 1200 mm/min

Stripping direction: 180 degree

Sample size: 25mm by 70mm

< evaluation of adhesive force after 80 ℃ X7 days >

Samples for initial adhesion evaluation were prepared separately, and the evaluation samples were left to stand at 80℃for 7 days. For the evaluation sample after storage (after the heat resistance test), the adhesive force was evaluated in the same manner as the initial adhesive force evaluation.

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

A laminated film was produced and evaluated in the same manner as in example 1, except that the perfluoropolyether compound (A1) was not added. The results are shown in Table 1.

TABLE 1

As is clear from the results of table 1, the laminated film using the adhesive composition containing the perfluoropolyether compound (A1) showed more excellent peeling property 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 containing no adhesion regulator (comparative example 2).

The perfluoroalkyl group-containing compound (a' 1) is a compound having a perfluorohexyl group, and thus is a compound having an environmental storage property that is a concern.

Claims (11)

1. An adhesive composition comprising: a perfluoropolyether compound (A) having a poly (perfluoroalkylene ether) chain (a 1), and a binder (B).

2. The adhesive composition according to claim 1, wherein the compound (a) has a polyoxyalkylene chain (a 2) and/or a silicone chain (a 3).

3. The adhesive composition according to claim 1 or 2, wherein the compound (a) is a polymer having a poly (perfluoroalkylene ether) chain (a 1) on the main chain, a polyoxyalkylene chain (a 2) and/or a silicone chain (a 3) on the side chain.

4. The adhesive composition according to any one of claims 1 to 3, wherein the compound (a) is a copolymer comprising, as a polymerization component, a polymerizable monomer having a poly (perfluoroalkylene ether) chain (a 1), and 1 or more kinds selected from the group consisting of a polymerizable monomer containing a polyoxyalkylene chain (a 2) and a polymerizable monomer containing a silicone chain (a 3).

5. The adhesive composition according to claim 4, wherein the polymerizable monomer having a poly (perfluoroalkylene ether) chain (a 1) is a compound having polymerizable unsaturated groups at both ends of the poly (perfluoroalkylene ether) chain (a 1).

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 6, wherein the compound (a) has no fluorinated alkyl group.

8. 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 mass% in the solid content of the adhesive composition.

9. 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).

10. A laminated film, comprising: an adhesive layer of the adhesive composition of any one of claims 1 to 9, and a substrate layer.

11. The laminated film according to claim 10, which is a surface protective film for an optical member.