KR20230051555A - Pressure-sensitive adhesive composition and laminated film using the same - Google Patents

Abstract

A pressure-sensitive adhesive composition having an excellent adhesive force adjusting effect and a laminated film that can be suitably used as a surface protection film by using the pressure-sensitive adhesive composition for a pressure-sensitive adhesive layer are provided. Specifically, an adhesive composition containing a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1) and an adhesive (B).

Description

Pressure-sensitive adhesive composition and laminated film using the same

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

On the surface of optical members such as polarizers, retardation plates, optical compensation films, and transparent conductive films used in liquid crystal displays, organic EL displays, touch panels, etc., an adhesive protective film is provided for surface protection during manufacturing, transportation, and use. is attached

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

When peeling the protective film from the adherend, it is required that the protective film can be peeled cleanly with a small force and that no adhesive residue (deposit) occurs on the surface of the adherend.

In recent years, for optical members used in large-sized displays, peeling of surface protection films by machines has become mainstream, and the peeling speed is often different depending on the process, and the peelability is better and the protective film with less adhesive remains. this is being requested

In the form of meeting the above requirements, development of a surface protection film having both a slight adhesiveness that can be peeled off even with a small force and a re-peelability that can be peeled off cleanly again even after sticking once has been developed (e.g., Patent Literature One).

Japanese Patent Laid-Open No. 2019-026707

The surface protection film using the adhesive composition of patent document 1 had the problem that peeling performance was not sufficient because the adhesive force adjustment effect of an adhesive composition was inadequate. Further, the pressure-sensitive adhesive composition described in Patent Literature 1 includes a compound having a fluorinated alkyl group having 6 carbon atoms, but the compound is a compound of which environmental accumulation is a concern.

An object to be solved by the present invention is to provide a pressure-sensitive adhesive composition having an excellent adhesive force adjusting effect and a laminated film that can be suitably used as a surface protection film by using the pressure-sensitive adhesive composition for an adhesive layer.

As a result of intensive studies, the inventors of the present invention have found that a pressure-sensitive adhesive composition containing a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1) and an adhesive (B) solves the above problems. found out what could be done, and completed the present invention.

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

ADVANTAGE OF THE INVENTION According to this invention, the laminated|multilayer film which can be used suitably as a surface protection film can be provided by using the adhesive composition excellent in adhesive force adjusting effect, and this for an adhesion layer.

Hereinafter, one embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range not impairing the effects of the present invention.

In addition, in this specification, "(meth)acrylate" refers to one or both of acrylate and methacrylate.

<Adhesive composition>

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

The perfluoropolyether compound (A) can function as an adhesive force modifier, and a laminated film having excellent peeling performance can be produced by using the pressure-sensitive adhesive composition of the present invention.

Hereinafter, each component contained in the pressure-sensitive adhesive composition of the present invention is described.

[Perfluoropolyether compound (A)]

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

The poly(perfluoroalkylene ether) chain (a1) of the compound (A) may have a structure in which divalent fluorohydrocarbon groups and oxygen atoms are alternately connected, and is represented by the following general formula (a1-1) can lift

(In the above formula (a1-1),

X is each independently a perfluoroalkylene group,

n1 is the number of iterations)

In some X, 2 or more types of perfluoroalkylene groups may exist randomly or in block form.

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

The perfluoroalkylene group of X is preferably a perfluoroalkylene group having 1 to 3 carbon atoms, more preferably a perfluoromethylene group or a perfluoroethylene group, and an industrially obtainable viscosity When included, more preferably, a perfluoromethylene group and a perfluoroethylene group coexist.

When the perfluoromethylene group (X-1) and the perfluoroethylene group (X-2) coexist, the abundance (X-1/X-2) (number ratio) is 1/10 to 10/ 1 is preferable, and 3/10 - 10/3 are more preferable.

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, still more preferably 6 to 100. It is an integer in the range of 70, and most preferably an integer in the range of 12 to 50.

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

The content ratio of the poly(perfluoroalkylene ether) chain (a1) of the compound (A) is, for example, in the range of 1 to 90% by mass, preferably in the range of 1 to 80% by mass, more preferably Preferably, it is in the range of 1 to 70% by mass.

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

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 adjustment function can be improved.

The polyoxyalkylene chain (a2) of the compound (A) is, for example, a plurality of alkylene chains having 1 to 6 carbon atoms such as polyoxyethylene, polyoxypropylene, and polyoxybutylene connected by ether bonds. Any one may be present, and the structure of the alkylene chain may be linear or branched.

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

(In the above formula (a2-1),

A plurality of R ^a2 are each independently an alkylene group having 1 to 6 carbon atoms;

n2 is the number of iterations)

In a plurality of R ^a2 , two or more types of alkylene groups may exist randomly or in block form.

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

When the polyoxyalkylene chain (a2) consists of a polyoxyethylene chain and a polyoxypropylene chain, the polyoxyethylene chain and polyoxypropylene chain in the polyoxyalkylene chain (a2) may exist randomly or exist in block form. You can do it.

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, still more preferably an integer in the range of 3 to 100. An integer in the range of 50.

The content of the polyoxyalkylene chain (a2) in the compound (A) is, for example, in the range of 1 to 90% by mass, preferably in the range of 1 to 80% by mass, and more preferably in the range of 1 to 70% by mass. range of %.

The content ratio of the polyoxyalkylene chain (a2) can be calculated and adjusted from the charged amount of a polymerizable monomer having a polyoxyalkylene chain (a2) described later.

The silicone chain (a3) of the compound (A) includes a group represented by the following formula (a3-1).

(In the above formula (a3-1),

A plurality of R ^a3 are each independently an alkyl group or a phenyl group having 1 to 18 carbon atoms;

n3 is the number of iterations)

The alkyl group of 1 to 18 carbon atoms in R ^a3 may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, and t -A butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group, etc. are mentioned.

The C1-C18 alkyl group of R ^a3 is preferably a C1-C6 alkyl group, more preferably a methyl group.

The number of repetitions 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 (a3) in 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. is the range

The content ratio of the silicone chain (a3) can be calculated and adjusted from the charged amount of the polymerizable monomer having the silicone chain (a3) described later.

Compound (A) preferably has a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1), a polymerizable monomer having a polyoxyalkylene chain (a2), and a polymerization having a silicone chain (a3) It is a copolymer which uses at least one type selected from the group consisting of sex monomers as a polymerization component.

Here, "polymerization component" means a component constituting the copolymer, and solvents and polymerization initiators that do not constitute the copolymer are not included.

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

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, more preferably poly(perfluoroalkylene ether) chain. It is a compound having a (meth)acryloyl group or a styryl group at both ends of a (perfluoroalkylene ether) chain.

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

Specific examples of the compound having a polymerizable unsaturated group at both ends of the poly(perfluoroalkylene ether) chain include compounds represented by the following formulas (A1-1) to (A1-13). In addition, PFPE in formulas (A1-1) to (A1-13) is a linking group represented by the formula (a1-1).

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

As a method for producing a compound having polymerizable unsaturated groups at both ends of a poly(perfluoroalkylene ether) chain, for example, a compound having one hydroxyl group at both ends of a poly(perfluoroalkylene ether) chain , Method obtained by dehydrochlorination of (meth)acrylic acid chloride, method obtained by reaction of (meth)acrylic acid anhydride, method obtained by dehydration of (meth)acrylic acid, urethanization of 2-(meth)acryloyloxyethyl isocyanate a method obtained by reaction, a method obtained by esterification of itaconic anhydride, a method obtained by reaction with styrene having a chloromethyl group in the presence of a base; A method obtained by subjecting a compound having one carboxy group at both ends of a poly(perfluoroalkylene ether) chain to an esterification reaction of 4-hydroxybutyl acrylate glycidyl ether, glycidyl (meth)acrylate Method obtained by esterification reaction; A method of reacting and introducing 2-hydroxyethyl (meth)acrylate with a compound having one isocyanate group at both ends of the poly(perfluoroalkylene ether) chain, and 2-hydroxyethyl (meth)acrylamide How to react can be mentioned.

Among these, a method obtained by subjecting a compound having one hydroxyl group to both terminals of a poly(perfluoroalkylene ether) chain to a dehydrochloric acid reaction of (meth)acrylic acid chloride, a method obtained by reacting a (meth)acrylic acid anhydride, or A method obtained by subjecting 2-(meth)acryloyloxyethyl isocyanate to a urethanization reaction is particularly preferred in view of synthetically obtaining it easily.

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).

(Among the above formulas (A2-1) and (A2-2),

R ^a21 , R ^a22 and R ^a23 are each independently an alkylene group having 1 to 6 carbon atoms;

R ^a24 is each independently a hydrogen atom or a methyl group;

R ^a25 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

p, q and r are each independently an integer greater than or equal to 0, and p+q+r is an integer greater than or equal to 1)

The C1-C6 alkylene groups of R ^a21 , R ^a22 and R ^a23 are preferably C2-C4 alkylene groups.

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, still more preferably 3 An integer in the range of ~50.

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

As the polymerizable monomer having a polyoxyalkylene chain (a2), commercially available products can be used, such as Brenma PE-90, Brenma PE-200, and Brenma, which are hydroxyl group-terminated polyalkylene glycol mono(meth)acrylates. Brenma PE-350, Brenma AE-90, Brenma AE-200, Brenma AE-400, Brenma PP-1000, Brenma PP-500, Brenma PP-800, Brenma AP-150, Brenma AP -400, Brenma AP-550, Brenma AP-800, Brenma 50PEP-300, Brenma 70PEP-350B, Brenma AEP Series, Brenma 55PET-400, Brenma 30PET-800, Brenma 55PET-800, Brenma AET series, Brenma 30PPT-800, Brenma 50PPT-800, Brenma 70PPT-800, Brenma APT series, Brenma 10PPB-500B, Brenma 10APB-500B (above, manufactured by Nichiyu Co., Ltd.); Brenma PME-100, Brenma PME-200, Brenmar PME-400, Brenmar PME-1000, Brenmar PME-4000, Brenma AME-400, which are alkyl-terminated polyalkylene glycol mono(meth)acrylates; Brenma 50POEP-800B, Brenma 50AOEP-800B, Brenma PLE-200, Brenma ALE-200, Brenma ALE-800, Brenma PSE-400, Brenma PSE-1300, Brenma ASEP Series, Brenma PKEP Series, Brenma AKEP series, Brenma ANE-300, Brenma ANE-1300, Brenma PNEP series, Brenma PNPE series, Brenma 43ANEP-500, Brenma 70ANEP-550 (above, made by Nichiyu 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, light acrylate NP-8EA (above, Koeisha Chemical Co., Ltd. make), etc. are mentioned.

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

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

(In the above formula (A3-1),

R ^a31 is each independently an alkyl group having 1 to 6 carbon atoms or a group represented by -OSi(R ^a34 ) ₃ (R ^a34 is each independently an alkyl group having 1 to 3 carbon atoms);

R ^a32 and R ^a33 are each independently an alkyl group 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 the number of iterations)

R ^a31 , R ^a32 and R ^a34 are preferably methyl groups.

R ^a33 is preferably a butyl group.

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

The alkylene group of 1 to 50 carbon atoms of L ¹ is preferably an alkylene group of 1 to 15 carbon atoms, more preferably an alkylene group of 1 to 5 carbon atoms, still more preferably a methylene group; It is an ethylene group, n-propylene group, or isopropylene group.

The C1-C50 alkyleneoxy group of L ¹ is, for example, a group in which -CH ₂ - in one of the C1-C50 alkylene groups is substituted for -O-.

The alkyleneoxy group of 1 to 50 carbon atoms in L ¹ is preferably an alkyleneoxy group of 1 to 15 carbon atoms, more preferably an alkyleneoxy group of 1 to 8 carbon atoms, still more preferably They are 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.

One or more substituents, such as a hydroxyl group, a phenyl group, and a phenoxy group, may substitute for the carbon atom which respectively comprises the alkylene group of 1-50 carbon atoms and the alkyleneoxy group of 1-50 carbon atoms of L ^<1> .

As the polymerizable monomer containing a silicone chain (a3), compounds represented by the following formulas (A3-2) to (A3-9) are also preferable.

(Among the above formulas (A3-2) to (A3-9),

m is an integer of 1-6 each independently.

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

R ^a32 is each independently an alkyl group having 1 to 6 carbon atoms.

R ^a33 is each independently an alkyl group having 1 to 6 carbon atoms.

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

The molecular weight of the polymerizable monomer 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.

As the polymerizable monomer containing the silicone chain (a3), commercially available products can be used.

The polymerizable monomer containing the silicone chain (a3) used as a polymerization component may be used individually by 1 type, or may use 2 or more types together.

Compound (A) is a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1), a polymerizable monomer having a polyoxyalkylene chain (a2), and a polymerizable monomer having a silicone chain (a3) Other polymerizable monomers may be used for the polymerizable component.

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

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, a normal propyl group, an isopropyl group, an n-butyl group, and t -A butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group, etc. are mentioned.

The C1-C18 alkyl group (a4) may be substituted with one or more substituents such as a hydroxyl group, a phenyl group, and a phenoxy group.

The alkyl group (a4) of 1 to 18 carbon atoms includes, for example, a hydroxyalkyl group of 1 to 18 carbon atoms, a phenylalkyl group of 7 to 18 carbon atoms, and a phenoxyalkyl group of 7 to 18 carbon atoms. do.

Examples of the aromatic group (a5) having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthren-1-yl group.

The aromatic group (a5) of 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 of 1 to 6 carbon atoms.

Examples of the polymerizable monomer having an alkyl group of 1 to 18 carbon atoms and a polymerizable unsaturated group having a (meth)acryloyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth )Acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, s-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, alkyl esters having 1 to 18 carbon atoms of (meth)acrylic acid, such as dodecyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; Dicyclopentanyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, and bridged cyclic alkyl esters having 1 to 18 carbon atoms of (meth)acrylic acid, such as dicyclopentanyl (meth)acrylate and dicyclopentenyl (meth)acrylate.

Examples of the polymerizable monomer having an alkyl group of 1 to 18 carbon atoms and having a vinyl ether group as the polymerizable unsaturated group include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, and 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, etc. of alkyl 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-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 of 1 to 18 carbon atoms and having an allyl group as the polymerizable unsaturated group include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether. there is.

As a polymerizable monomer which has a C1-C18 alkyl group and whose polymerizable unsaturated group is a (meth)acryloylamide group, for example, N,N-dimethylacrylamide, N,N-diethylacrylamide, N -Isopropyl acrylamide, diacetone acrylamide, acroyl morpholine, etc. are mentioned.

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

Examples of the polymerizable monomer having a hydroxyalkyl group of 1 to 18 carbon atoms and a polymerizable unsaturated group having 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, 2,3-dihydroxypropyl (meth)acrylate etc. are mentioned.

Examples of the polymerizable monomer having a phenylalkyl group of 7 to 18 carbon atoms or a phenoxyalkyl group of 7 to 18 carbon atoms and a polymerizable unsaturated group having a (meth)acryloyl group include benzyl (meth)acrylate; 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc. are mentioned.

As a polymerizable monomer which has an aromatic group of 6-18 carbon atoms, styrene, (alpha)-methylstyrene, p-methylstyrene, p-methoxy styrene etc. are mentioned, for example.

The said other monomer used as a polymerization component may be used individually by 1 type, and may use 2 or more types together.

Compound (A) is a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) and a polymerizable monomer other than a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) ( In the case of a copolymer having a polymerizable monomer having a polyoxyalkylene chain (a2), a polymerizable monomer having a silicone chain (a3), and any other polymerizable monomer) as a polymerization component, the polymerization form is not particularly limited.

Any of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer may be sufficient as the said copolymer, for example.

The charge ratio of each polymerizable monomer described above is not particularly limited.

The amount of the polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1) is, for example, in the range of 1 to 90% by mass, preferably in the range of 1 to 80% by mass, More preferably, it is the range of 1-70 mass %.

Compound (A) is a polymerizable monomer containing a poly(perfluoroalkylene ether) chain (a1), a polymerizable monomer containing a polyoxyalkylene chain (a2), and a silicone chain (a3). In the case of a copolymer comprising at least one selected from the group consisting of monomers as a polymerization component, polyoxyalkylene chain (a2) with respect to 100 parts by mass of polymerizable monomer having poly(perfluoroalkylene ether) chain (a1) The total amount of the polymerizable monomer containing and the polymerizable monomer containing the silicone chain (a3) is, for example, in the range of 5 to 2,000 parts by mass, preferably in the range of 10 to 2,000 parts by mass, and more preferably in the range of 15 to 2,000 parts by mass. It is in the range of 2,000 parts by mass.

Compound (A) is preferably a polymer containing a poly(perfluoroalkylene ether) chain (a1) in its main chain and a polyoxyalkylene chain (a2) and/or a silicone chain (a3) in its side chain. .

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

Compound (A) is preferably a polymerizable monomer having a polymerizable unsaturated group at both ends of the poly(perfluoroalkylene ether) chain (a1), a polymerizable monomer containing a polyoxyalkylene chain (a2), and It is a copolymer which uses, as a polymerization component, at least one member selected from the group consisting of polymerizable monomers containing a silicone chain (a3).

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

When the compound (A) does not contain a perfluoroalkyl group having 6 or more carbon atoms, the environmental load can be reduced.

In addition, the "perfluoroalkyl group having 6 or more carbon atoms" here does not include a poly(perfluoroalkylene ether) chain.

Compound (A) preferably does not have a fluorinated alkyl group.

By not having a fluorinated alkyl group, the compound (A) 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 3,000 to 300,000 from the viewpoints of compatibility with the pressure-sensitive adhesive (B) described later, ease of adjusting the adhesive force, and coexistence of reducing sticking, etc. It is more preferably in the range of 3,000 to 200,000, and 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 such as a large-area optical member.

The weight average molecular weight in the present invention is a value obtained by measuring by the method described in Examples.

The method for producing the compound (A) is not particularly limited, and can be produced by a known method.

Compound (A) can be produced by a solution polymerization method, bulk polymerization method, emulsion polymerization method or the like based on a polymerization mechanism such as radical polymerization method, cationic polymerization method, anionic polymerization method, but radical polymerization method is particularly convenient, industrially desirable. For example, it can be manufactured by adding a general-purpose radical polymerization initiator to a polymerizable monomer mixture in an organic solvent and polymerizing it.

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

Various types of polymerization initiators can be used, and examples thereof include peroxides such as benzoyl peroxide and diacyl peroxide, azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenyl azotriphenylmethane; metal chelate compounds such as (acac) ₃ , transition metal catalysts that cause living radical polymerization, and the like.

If necessary, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, and octylthioglycolic acid, and thiol compounds having coupling groups such as γ-mercaptopropyltrimethoxysilane as chain transfer agents You may use it as an additive, such as.

Polymerization can be carried out either in the presence or absence of a solvent, but it is preferably carried out in the presence of a solvent from the viewpoint of workability.

Examples of the solvent used for polymerization include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol, 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, butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, 2-methoxy Monocarboxylic acid esters such as methyl propionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, and 2-methoxybutylpropionate, polar solvents such as dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone, methyl Cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethers such as ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Propylene glycol and its esters such as glycol monobutyl ether acetate, halogen solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, benzene, toluene, xylene, etc. aromatics, and further fluorinated inert liquids such as perfluorooctane and perfluorotri-n-butylamine.

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

The solvent used for polymerization of compound (A) may be the solvent of the pressure-sensitive adhesive composition of the present invention.

[Adhesive (B)]

As the adhesive (B), any adhesive can be used without particular limitation as long as it has adhesive properties, and examples thereof include acrylic adhesives, urethane adhesives, synthetic rubber adhesives, natural rubber adhesives, and silicone adhesives. Among these adhesives, it is preferable to use an acrylic adhesive (b1) and/or a urethane adhesive (b2).

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

1 type or 2 or more types can be used for the said (meth)acrylic monomer as a main component. By using the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, it becomes easy to control the adhesive force to the adherend (substrate) to a low level, and a surface protection film excellent in easy peelability and re-peelability is obtained

Further, the "main component" in the present invention means the most component among the total amount of constituent components, and the "main component" preferably exceeds 40% by mass, more preferably exceeds 50% by mass, More preferably, it means exceeding 60% by mass.

Examples of the (meth)acrylic monomer having an alkyl group of 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and s-butyl (meth)acrylate. ) 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, n-tetradecyl (meth)acrylate, etc. are mentioned.

Among the above (meth)acrylic monomers, 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 A (meth)acrylic monomer having an alkyl group having 6 to 14 carbon atoms, such as (meth)acrylate, is preferable from the viewpoint of making it easy to control the adhesive force to an adherend to a low level and providing excellent re-peelability.

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

It is preferable that the (meth)acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) contains a (meth)acrylic monomer having a hydroxyl group as a raw material monomer. 1 type or 2 or more types can be used as a (meth)acrylic-type monomer which has the said hydroxyl group.

By using the (meth)acrylic monomer having the above hydroxyl group, it becomes easy to control the crosslinking of the pressure-sensitive adhesive composition, and furthermore, it is easy to control the balance between the improvement of the wettability due to flow and the reduction of the adhesive force during peeling, and also antistatic It is also desirable from the point of view of

Examples of the (meth)acrylic monomer having the hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyethyl (meth)acrylate. Hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclo Hexyl) methyl (meth)acrylate, N-methylol (meth)acrylamide, etc. are mentioned. In particular, it is preferable to use a (meth)acrylic monomer having a hydroxyl group having 4 or more carbon atoms in the alkyl group, since easy peeling at the time of high-speed peeling becomes easy.

With respect to 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, it is preferable to contain 15 parts by mass or less of the (meth)acrylic monomer having the hydroxy group, more preferably 1 to 13 Part by mass, more preferably 2 to 10 parts by mass, most preferably 3 to 8 parts by mass. When it exists in the said range, since it becomes easy to control the balance of the wettability of an adhesive composition, and the cohesion force of the adhesive layer obtained, it is preferable.

Polymerization for adjusting the glass transition temperature and peelability of (meth)acrylic polymers by setting the Tg to 0°C or less (usually -100°C or more) as another polymerizable monomer component for easy balance of adhesive performance. A sex monomer etc. can be used.

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

As a (meth)acrylic-type monomer which has the said carboxy group, (meth)acrylic acid, carboxylethyl (meth)acrylate, carboxylpentyl (meth)acrylate etc. are mentioned, for example.

The (meth)acrylic monomer having a carboxyl group is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, based on 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, It is more preferably less than 1 part by mass, even more preferably less than 0.2 part by mass, and most preferably 0.01 part by mass or more and less than 0.1 part by mass. If it is within the above range, it is possible to prevent an increase in adhesive force due to lapse of time (adhesive force increase prevention property), and is preferable.

It is also possible to use the (meth)acrylic monomer having a hydroxyl group and the (meth)acrylic monomer having a carboxyl group in combination for the purpose of achieving both peeling charging characteristics and adhesive strength increase prevention.

In addition, 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 used in the above (meth)acrylic polymer. As other polymerizable monomers, it can be used without particular limitation. For example, components for improving cohesion and heat resistance such as cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, N-acryloylmorpholine , A component having a functional group that acts as an adhesive strength improvement or crosslinking starting point, such as a vinyl ether monomer, can be appropriately used. Among them, it is preferable to use a cyano group-containing monomer, an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, and a nitrogen-containing monomer such as N-acryloylmorpholine. By using a nitrogen-containing monomer, it is useful because it is possible to secure appropriate adhesive strength that does not cause lifting or peeling, and to obtain a surface protection film with more excellent shear force. These polymerizable monomers may be used independently, and may mix and use 2 or more types.

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 styrene.

Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethyl acrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N -Diethylacrylamide, N,N-diethylmethacrylamide, N,N'-methylenebisacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, diacetone acrylamide Amide etc. are mentioned.

As said imide group containing monomer, cyclohexyl maleimide, isopropyl maleimide, N-cyclohexyl maleimide, itaconimide etc. are mentioned, for example.

Examples of the amino group-containing monomer include aminoethyl (meth)acrylate, N,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, and allyl glycidyl ether.

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

Other polymerizable monomers other than the (meth)acrylic monomer having an alkyl group of 1 to 14 carbon atoms, the (meth)acrylic monomer having a hydroxyl group, and the (meth)acrylic monomer having a carboxyl group include the alkyl group having 1 to 14 carbon atoms It is preferably 0 to 40 parts by mass, and preferably 0 to 30 parts by mass, with respect to 100 parts by mass of the (meth)acrylic monomer having .

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

The average c of 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, and particularly 5 to 30 desirable.

When the average added mole number is 1 or more, the effect of reducing contamination of the adherend (object to be protected) tends to be obtained efficiently. Moreover, when the said average added mole number is larger than 40, the viscosity of an adhesive composition rises and coating tends to become difficult. In addition, the terminal of the oxyalkylene chain may be substituted with a hydroxy group as it is or with another functional group or the like.

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

Examples of the oxyalkylene unit of the polyoxyalkylene chain-containing reactive monomer include those 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. etc. can be mentioned. The hydrocarbon group of the oxyalkylene chain may be straight chain or may be branched.

It is more preferable that the said polyoxyalkylene chain containing reactive monomer is a reactive monomer which has an ethylene oxide group. By using a (meth)acrylic polymer having a reactive monomer having an ethylene oxide group as the base polymer, compatibility between the base polymer and the perfluoropolyether compound (A) is improved, and bleed to an adherend is suitably suppressed. , it is easy to obtain a low-staining pressure-sensitive adhesive composition.

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

As a specific example of the said (meth)acrylic-acid alkylene oxide adduct, for example, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polyethylene glycol-poly Butylene glycol (meth)acrylate, polypropylene glycol-polybutylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, ethoxy polyethylene glycol (meth)acrylate, butoxy polyethylene glycol (meth) Acrylates, octoxypolyethylene glycol (meth)acrylate, lauroxypolyethylene glycol (meth)acrylate, stearoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth) ) acrylate, octoxy polyethylene glycol-polypropylene glycol (meth)acrylate, and the like.

Moreover, as a specific example of the said reactive surfactant, anionic reactive surfactant, nonionic reactive surfactant, cationic reactive surfactant etc. which have a (meth)acryloyl group or an allyl group are mentioned, for example.

The (meth)acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) has a weight average molecular weight (Mw) of preferably 100,000 to 5,000,000, more preferably 200,000 to 2,000,000, still more preferably 300,000 to 800,000. all. When the weight average molecular weight is larger than 100,000, the cohesive force of the pressure-sensitive adhesive layer becomes appropriate and there is a tendency to suppress pasting. On the other hand, when the weight average molecular weight is 5,000,000 or less, the fluidity of the polymer is appropriate, wetting to the adherend is sufficient, and blisters generated between the adherend and the pressure-sensitive adhesive layer of the surface protection film are suppressed can do.

In addition, the said weight average molecular weight says what was obtained by measuring by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the (meth)acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) is preferably 0°C or lower, more preferably -10°C or lower (usually -100°C or higher). When the glass transition temperature is higher than 0°C, the polymer tends to be difficult to flow, resulting in insufficient wetting. In particular, by setting the glass transition temperature to -61°C or lower, an adhesive layer excellent in wettability and easy peelability can be easily obtained.

In addition, the glass transition temperature of the (meth)acrylic polymer can be adjusted within the above range by appropriately changing the monomer component and composition ratio to be used.

The polymerization method of the (meth)acrylic polymer is not particularly limited, and polymerization can be performed by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, or suspension polymerization. From the point of view of properties such as low contamination of the protective body), solution polymerization is a more preferable embodiment. Moreover, any, such as a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer, may be sufficient as the polymer obtained.

When using the urethane-based adhesive (b2) as the adhesive (B), any suitable urethane-based adhesive may be employed. As the urethane-based pressure-sensitive adhesive (b2), those made of a urethane resin (urethane-based polymer) obtained by reacting a polyol and a polyisocyanate compound are preferably exemplified.

As said polyol, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol etc. are mentioned, for example.

As said polyisocyanate compound, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate etc. are mentioned, for example.

In the case of using a silicone-based pressure-sensitive adhesive for the pressure-sensitive adhesive layer, any appropriate silicone-based pressure-sensitive adhesive may be employed. As such a silicone pressure-sensitive adhesive, one obtained by blending or aggregating a silicone resin (silicone-based polymer, silicone component) can be preferably employed.

Moreover, as said silicone type adhesive, addition reaction hardening type silicone type adhesive and peroxide curing type silicone type adhesive are mentioned. Among these silicone-based pressure-sensitive adhesives, addition reaction-curing type silicone-based pressure-sensitive adhesives are preferable because peroxides (such as benzoyl peroxide) are not used and decomposition products are not generated.

As the curing reaction of the addition reaction-curing type silicone pressure-sensitive adhesive, for example, when obtaining a polyalkylsilicone-based pressure-sensitive adhesive, a method of curing the polyalkylhydrogensiloxane composition with a platinum catalyst is generally exemplified.

In the pressure-sensitive adhesive composition of the present invention, the blending ratio of the perfluoropolyether compound (A) and the pressure-sensitive adhesive (B) may be appropriately set according to the desired adhesive strength. When the pressure-sensitive adhesive composition of the present invention is used for the pressure-sensitive adhesive layer of a surface protection film, the content of the perfluoropolyether compound (A) is preferably 0.01 to 20% by mass, and preferably 0.1 to 5.0% by mass in the solid content of the pressure-sensitive adhesive composition. it is more preferable Within this range, the perfluoropolyether compound (A) can sufficiently exhibit its function as an adhesive strength modifier.

Moreover, in this invention, "solid content" means the component from which the solvent was removed from the adhesive composition.

[Other Ingredients]

The pressure-sensitive adhesive composition of the present invention should just contain the perfluoropolyether compound (A) and the pressure-sensitive adhesive (B), and may optionally contain other components such as various additives within a range that does not impair the effects of the present invention. .

It is preferable that the adhesive composition of this invention contains a crosslinking agent as another component. For example, when the pressure-sensitive adhesive composition of the present invention contains the (meth)acrylic polymer as the pressure-sensitive adhesive (B), by further including a crosslinking agent, the structural unit of the (meth)acrylic polymer, the composition ratio, and the selection of the crosslinking agent And by crosslinking by appropriately adjusting the addition ratio, etc., a pressure-sensitive adhesive layer having more excellent heat resistance can be easily obtained.

As the crosslinking agent, an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, a metal chelate compound, or the like may be used, and the use of an isocyanate compound is particularly preferable. In addition, these compounds may be used independently, and may mix and use 2 or more types.

Examples of the isocyanate compound include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate. Alicyclic isocyanates such as isocyanate (IPDI), aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate (XDI), and allophanates of these isocyanate compounds. Modified polyisocyanate modified by a 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 is exemplified.

Commercially available products of the above isocyanate compounds include, for example, trade names: Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (above, manufactured by Takedaya Chemical Industry Co., Ltd.), Sumidul T80, Sumidul L, Death Module N3400 (above, manufactured by Sumika Baier Urethane Co., Ltd.), Myrionate MR, Myrionate MT, Coronate L, Coronate HL, Coronate HX (above, manufactured by Nippon Polyurethane Kogyo Co., Ltd.), and the like.

These isocyanate compounds may be used independently, may be used in mixture of 2 or more types, and it is also possible to use a bifunctional isocyanate compound and a trifunctional or more than trifunctional isocyanate compound in combination. By using a mixture of two or more types of crosslinking agents, it becomes possible to achieve both adhesiveness and repelling resistance (adhesion to a curved surface), and a laminated film having more excellent adhesion reliability can be obtained.

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

As said melamine-type resin, hexamethylol melamine etc. are mentioned.

Examples of the aziridine derivatives include commercially available products under trade names HDU, TAZM, and TAZO (above, manufactured by Sogo Chemical Co., Ltd.).

As said metal chelate compound, aluminum, iron, tin, titanium, nickel etc. are mentioned as a metal component, Acetylene, methyl acetoacetate, ethyl lactate, etc. are mentioned as a chelate component.

The content of the crosslinking agent is, for example, preferably 0.01 to 20 parts by mass, and preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the (meth)acrylic polymer used in the acrylic pressure-sensitive adhesive (b1). It is more preferable, and it is more preferable that it contains 0.5-10 mass parts, and it is most preferable that it contains 1.0-6 mass parts. By using a crosslinking agent within this range, the cohesive force of the pressure-sensitive adhesive layer obtained is appropriate, sufficient heat resistance is easily obtained, and adhesive residue is also suppressed.

A crosslinking agent may be used individually by 1 type, and may mix and use 2 or more types.

The pressure-sensitive adhesive composition may contain a crosslinking catalyst for more effectively advancing any of the crosslinking reactions described above.

Examples of the crosslinking catalyst include tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris(acetylacetonato)iron, tris(hexane-2,4-dionato)iron, and tris(heptane). -2,4-dionato) iron, tris (heptane-3,5-dionato) iron, tris (5-methylhexane-2,4-dionato) iron, tris (octane-2,4-dionato) Iron, tris(6-methylheptane-2,4-dionato)iron, tris(2,6-dimethylheptane-3,5-dionato)iron, tris(nonane-2,4-dionato)iron, tris (nonane-4,6-dionato) iron, tris (2,2,6,6-tetramethylheptane-3,5-dionato) iron, tris (tridecane-6,8-dionato) iron, tris (1-phenylbutane-1,3-dionato)iron, tris(hexafluoroacetylacetonato)iron, tris(ethylacetoacetate)iron, tris(acetoacetate-n-propyl)iron, tris(isoacetoacetate) Propyl) iron, tris(acetoacetate-n-butyl) iron, tris(acetoacetate-sec-butyl) iron, tris(acetoacetate-tert-butyl) iron, tris(propionylmethylacetate) iron, tris(propionyl) Ethyl acetate) iron, tris(propionylacetate-n-propyl)iron, tris(propionylisopropylacetate)iron, tris(propionylacetate-n-butyl)iron, tris(propionylacetate-sec-butyl)iron , tris(propionyl acetate-tert-butyl) iron, tris(benzyl acetoacetate) iron, tris(dimethyl malonate) iron, tris(diethyl malonate) iron, trimethoxy iron, triethoxy iron, triisopropanol Iron-based catalysts such as iron oxide and ferric chloride can be used. One type of these crosslinking catalysts may be sufficient, and they may use 2 or more types together.

The content of the crosslinking catalyst is not particularly limited, but 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. When it exists in the said range, when forming an adhesive layer, the speed of crosslinking reaction is fast and the pot life of an adhesive composition also becomes long, and it becomes a preferable aspect.

<Laminated film>

The laminated film of the present invention has an adhesive layer and a substrate 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 applying and crosslinking the pressure-sensitive adhesive composition of the present invention on at least one surface of the substrate layer. Moreover, the laminated|multilayer film of this invention can also be manufactured by transferring the adhesive layer which crosslinked the adhesive composition of this invention previously on at least one surface of a base material layer.

The method of forming the pressure-sensitive adhesive layer on the base layer is not particularly limited, but for example, it is produced by applying the pressure-sensitive adhesive composition (solution) of the present invention to a base material, drying and removing the polymerization solvent, etc. to form the pressure-sensitive adhesive layer on the base material. . Thereafter, curing may be performed for the purpose of adjusting migration of components in the pressure-sensitive adhesive layer or adjusting crosslinking reaction.

When applying the pressure-sensitive adhesive composition onto a base material to produce a laminated film, one or more solvents other than the polymerization solvent may be newly added to the pressure-sensitive adhesive composition so that the pressure-sensitive adhesive composition can be applied uniformly on the base material layer.

As a formation method of the adhesive layer at the time of manufacturing the laminated|multilayer film of this invention, the well-known method used for manufacture of adhesive tapes is used. Specifically, for example, roll coating, gravure coating, reverse coating, roll brush coating, spray coating, air knife coating method, extrusion coating method using a die coater, etc. are exemplified.

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

The laminated film of the present invention preferably has a total thickness of 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 the above range, the adhesive properties (repeelability, adhesiveness, etc.), workability, and appearance characteristics are excellent, which is a preferable aspect.

Moreover, "total thickness" means the sum total of the thickness including all layers, such as a base material layer, an adhesive layer, and an antistatic layer, of laminated|multilayer film.

The substrate layer constituting the laminated film of the present invention is not particularly limited, but, for example, it is preferable to use a substrate having excellent properties such as transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, flexibility, and dimensional stability. desirable. In particular, since the base material has flexibility, the pressure-sensitive adhesive composition can be applied using a roll coater or the like and can be rolled up, which is useful.

What can be used as the base material is, for example, polyester-based polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate; cellulosic polymers such as diacetyl cellulose and triacetyl cellulose; polycarbonate-based polymers; acrylic polymers such as polymethyl methacrylate; and the like as a main resin component (the main component in the resin component, typically a component that accounts for 50% by mass or more).

Other examples of the resin material include styrenic polymers such as polystyrene and acrylonitrile-styrene copolymer; olefinic polymers such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; vinyl chloride-based polymers; amide polymers such as nylon 6, nylon 6,6, and aromatic polyamide; What makes the etc. a resin material is mentioned.

As further examples of the resin material, imide-based polymers, sulfone-based polymers, polyether sulfone-based polymers, polyether ether ketone-based polymers, polyphenylene sulfide-based polymers, vinyl alcohol-based polymers, vinylidene chloride-based polymers, vinyl butyric acid A ral type polymer, an arylate type polymer, a polyoxymethylene type polymer, an epoxy type polymer, etc. are mentioned.

It may be a substrate composed of a blend of two or more of the polymers described above.

As the substrate, a plastic film made of a transparent thermoplastic resin material can be preferably employed. Among the above plastic films, it is a more preferable aspect to use a polyester film. 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 the main resin component. say to do Such a polyester film has properties desirable as a substrate for a surface protection film, such as excellent optical properties and dimensional stability.

Various additives such as antioxidants, ultraviolet absorbers, plasticizers, colorants (pigments, dyes, etc.), antistatic agents, and antiblocking agents may be incorporated into the resin material constituting the base material as necessary. In addition, the surface of the film used as the base material may be subjected to a known or customary surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, or application of an undercoat agent.

The laminated film of the present invention may have an antistatic layer on the substrate layer, and it is also possible to use a plastic film subjected to antistatic treatment as the substrate. By using such a base material, the film itself is prevented from being charged when it is peeled off, so it is preferable.

In addition, the base material is a plastic film, and antistatic treatment is applied to the plastic film to reduce the static charge of the laminated film itself and to obtain an excellent antistatic ability to adherends. In addition, the method for imparting the antistatic function is not particularly limited, and conventionally known methods can be used. For example, an antistatic resin composed of an antistatic agent and a resin component, a conductive polymer, or a conductive material containing a conductive material. A method of applying a resin, a method of vapor deposition or plating of a conductive material, a method of incorporating an antistatic agent or the like, and the like are exemplified. When using an antistatic agent, you may use a lubricant together.

The thickness of the substrate layer is usually about 5 to 200 μm, preferably about 10 to 100 μm. When the thickness of the base material layer is within the above range, it is preferable because it is excellent in bonding workability to an adherend and peeling workability in the adherend.

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

As the material constituting the separator, there are paper and plastic film, but a plastic film is preferably used because of its excellent surface smoothness. The film is not particularly limited as long as it is a film capable of protecting the pressure-sensitive adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride film. A copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, etc. are mentioned.

The thickness of the separator is usually about 5 to 200 μm, preferably about 10 to 100 μm. When it is within the above range, it is preferable because it is excellent in bonding workability to the pressure-sensitive adhesive layer and peeling workability in the pressure-sensitive adhesive layer. If necessary, the separator may be subjected to release and antifouling treatment using a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, or the like, or antistatic treatment such as coating, lead-in, or vapor deposition.

The laminated|multilayer film of this invention can be used conveniently as surface protection films, such as an optical member. The laminated film of the present invention is also excellent in stability over time and can be used for surface protection applications such as processing, conveyance, and shipping, so it is useful for applications that protect surfaces of optical members such as polarizing plates.

[Example]

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

In addition, this invention is not limited to the following example. In addition, "parts" and "%" in the following descriptions and tables are based on mass and represent solid content or active ingredients unless otherwise specified.

In Examples and Comparative Examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values obtained in terms of polystyrene based on gel permeation chromatography (GPC) measurement.

The measurement conditions of GPC are as follows.

[GPC measurement conditions]

Measuring device: Tosoh Corporation's high-speed GPC device "HLC-8320GPC"

Column: Tosoh Corporation "TSK GUARDCOLUMN SuperHZ-L" + Tosoh Corporation "TSKgel SuperHZM-N" + Tosoh Corporation "TSKgel SuperHZM-N" + Tosoh Corporation "TSKgel" SuperHZM-N” + “TSKgel SuperHZM-N” manufactured by Tosoh Corporation

Detector: RI (Differential Refractometer)

Data processing: Tosoh Corporation "EcoSECDataAnalysis Ver. 1.07"

Column temperature: 40°C

Developing solvent: tetrahydrofuran

Flow rate: 0.35mL/min

Measurement sample: A solution obtained by dissolving 7.5 mg of the sample in 10 ml of tetrahydrofuran and filtering the obtained solution with a microfilter was used as a measurement sample.

Sample injection volume: 20 μl

Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of "HLC-8320GPC" described above.

(monodisperse polystyrene)

"A-300" made by Toso Co., Ltd.

"A-500" made by Tosoh Corporation

"A-1000" manufactured by Tosoh Corporation

"A-2500" by Tosoh Corporation

"A-5000" by Tosoh Corporation

"F-1" made by Toso Co., Ltd.

"F-2" made by Toso Co., Ltd.

"F-4" made by Toso Co., Ltd.

"F-10" made by Toso Co., Ltd.

"F-20" made by Toso Co., Ltd.

"F-40" made by Toso Co., Ltd.

"F-80" made by Toso Co., Ltd.

"F-128" made by Toso Co., Ltd.

"F-288" made by Toso Co., Ltd.

(Synthesis Example 1: Synthesis of perfluoropolyether compound)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 20 g of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (a1-1-1) and 20 g of diisopropyl ether as a solvent 0.02 g of p-methoxyphenol as a polymerization inhibitor and 3.1 g of triethylamine as a neutralizer were added, stirring was started under an air stream, and 2.7 g of acrylic acid chloride was added dropwise over 1 hour while maintaining the inside of the flask at 10°C. did.

After completion of the dropwise addition, the mixture was reacted by stirring at 10°C for 1 hour, raising the temperature and stirring at 30°C for 1 hour, then raising the temperature to 50°C and stirring for 10 hours. Disappearance of acrylic acid chloride was confirmed in the obtained reaction liquid by gas chromatography measurement.

(In the expression,

A plurality of X's are each independently a perfluoromethylene group or a perfluoroethylene group, and per molecule, there are an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, The average number is 46.

The number average molecular weight by GPC is 1,500)

Next, 40 g of diisopropyl ether and 80 g of ion-exchanged water were added to the reaction solution as a solvent, stirred, then allowed to stand, and washing to remove the separated water layer was repeated three times. To the reaction solution after washing, 0.02 g of p-methoxyphenol was added as a polymerization inhibitor, 8 g of magnesium sulfate was added as a dehydrating agent, and the reaction solution was completely dehydrated by standing for one day, and the dehydrating agent was separated by filtration.

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

(In the expression,

A plurality of X's are each independently a perfluoromethylene group or a perfluoroethylene group, and per molecule, there are an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, number averages 46)

297.5 g of butyl acetate was introduced as a solvent into a glass flask equipped with a stirring device, a thermometer, a cooling pipe, and a dropping device, and the temperature was raised to 105°C while stirring under a nitrogen stream. Next, 24.9 g of the compound (A1-1), 5.9 g of a monomethacrylate compound (number average molecular weight: 5,000) having a polysiloxane bond represented by the following formula (A1-2), and a monoacrylate compound having an ethylene oxide chain (Nichiyu Co., Ltd., Brenmar AE-400, repeating number of ethylene oxide chain is about 10) 6.2 g, ethyl acrylate 50.4 g, 4-hydroxybutyl acrylate 12.6 g, butyl acetate 133.3 g as solvent, radical polymerization A liquid mixture was prepared by mixing 3.0 g of t-butylperoxy-2-ethylhexanoate as an initiator.

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

(In the above formula (A1-2), the number average of n2 is 65)

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

(Synthesis Example 2: Synthesis of perfluoroalkyl group-containing compound)

100 g of butyl acetate was put into 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 a monomethacrylate compound having a polysiloxane bond represented by the above formula (A1-2), and an ethylene oxide chain represented by the following formula (A2-1) 6.2 g of a monoacrylate compound, 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 t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator were mixed. Thus, a mixed solution was prepared.

The obtained liquid mixture was added dropwise to the glass flask at 95°C over 3 hours. After completion of the dropping, the mixture was stirred at 95°C for 3 hours and then stirred at 110°C for 1.0 hour. Then, it cooled, and the solution containing 30 mass % of perfluoroalkyl group-containing compound (A'1) was obtained.

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

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

Example 1

2.9 parts of D-100K (made by DIC Co., Ltd.) as a curing agent (crosslinking agent) and the obtained perfluoropolyether compound (A1 ) was added, diluted with methyl ethyl ketone to a solid content of 35%, and sufficiently mixed to obtain an adhesive composition.

The obtained pressure-sensitive adhesive composition was directly coated on the corona-treated surface of a 50-μm-thick polyester film as a base material using an automatic coating device bar coater (PI-1210: manufactured by Tester Co., Ltd.) so that the thickness of the adhesive layer after formation was 20 μm. . Then, after drying at 85°C for 3 minutes to form an adhesive layer, the adhesive layer was covered with a polyester film separator having a thickness of 38 μm coated with silicone to prepare a laminated film. This laminated film was further cured at 40°C for 3 days, and was used as a sample for an evaluation test.

The following evaluation was performed about the obtained laminated|multilayer film. The results are shown in Table 1.

<Evaluation of initial adhesive force>

The obtained laminated film was press-bonded and adhered to a glass plate by one reciprocation of a 2 kgf roller to obtain an evaluation sample. Twenty-four hours after the application, the adhesive strength of the evaluation sample was measured using an adhesion/film peeling analyzer VPA-3 (manufactured by Kyowa Interface Science Co., Ltd.). Measurement conditions are as follows. Adhesion was evaluated by two patterns: when the tensile speed and peeling speed were 150 mm/min, and when the tensile speed and peeling speed were 1,200 mm/min.

·Tension speed: 150mm/min, 1,200mm/min

Peeling speed: 150 mm/min, 1,200 mm/min

·Peel direction: 180˚

・Sample size: 25mm×70mm

<Evaluation of adhesive force after 80 ° C × 7 days>

A sample used for initial adhesive force evaluation was prepared separately, and the evaluation sample was placed at a temperature of 80°C and stored for 7 days. The adhesive force of the evaluation sample after storage (after the heat resistance test) was evaluated by the same method as the initial adhesive force evaluation.

Comparative Example 1

A laminated film was prepared 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 prepared 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]

From the results in Table 1, the laminated film using the pressure-sensitive adhesive composition containing the perfluoropolyether compound (A1) is the laminated film using the pressure-sensitive adhesive composition containing the perfluoroalkyl group-containing compound (A'1) (Comparative Example 1). ) and the adhesive composition not containing an adhesive force modifier.

In addition, since the perfluoroalkyl group-containing compound (A'1) is a compound having a perfluorohexyl group, it is a compound of concern about environmental accumulation.

Claims (11)

An adhesive composition comprising a perfluoropolyether compound (A) having a poly(perfluoroalkylene ether) chain (a1) and an adhesive (B). According to claim 1,
The adhesive composition in which the said compound (A) has a polyoxyalkylene chain (a2) and/or a silicone chain (a3). According to claim 1 or 2,
The pressure-sensitive adhesive composition wherein the compound (A) is a polymer having a poly(perfluoroalkylene ether) chain (a1) as a main chain and a polyoxyalkylene chain (a2) and/or a silicone chain (a3) as a side chain. According to any one of claims 1 to 3,
The compound (A) is a polymerization comprising a polymerizable monomer having a poly(perfluoroalkylene ether) chain (a1), a polymerizable monomer containing a polyoxyalkylene chain (a2), and a silicone chain (a3) A pressure-sensitive adhesive composition comprising, as a polymerization component, at least one selected from the group consisting of sex monomers. According to claim 4,
An adhesive composition in which the polymerizable monomer having the poly(perfluoroalkylene ether) chain (a1) is a compound having polymerizable unsaturated groups at both ends of the poly(perfluoroalkylene ether) chain (a1). According to any one of claims 1 to 5,
The adhesive composition in which the compound (A) does not have a perfluoroalkyl group having 6 or more carbon atoms. According to any one of claims 1 to 6,
The pressure-sensitive adhesive composition wherein the compound (A) does not have a fluorinated alkyl group. According to any one of claims 1 to 7,
The adhesive composition in which the content rate of the said compound (A) is the range of 0.01-20 mass % in the solid content of an adhesive composition. According to any one of claims 1 to 8,
A pressure-sensitive adhesive composition wherein the pressure-sensitive adhesive (B) is an acrylic pressure-sensitive adhesive (b1) and/or a urethane pressure-sensitive adhesive (b2). Laminate|multilayer film which has the adhesive layer of the adhesive composition in any one of Claims 1-9, and a base material layer. According to claim 10,
A laminated film that is a surface protection film for an optical member.