WO2022070933A1 - 粘着剤組成物、及びこれを用いた積層フィルム - Google Patents
粘着剤組成物、及びこれを用いた積層フィルム Download PDFInfo
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- WO2022070933A1 WO2022070933A1 PCT/JP2021/034025 JP2021034025W WO2022070933A1 WO 2022070933 A1 WO2022070933 A1 WO 2022070933A1 JP 2021034025 W JP2021034025 W JP 2021034025W WO 2022070933 A1 WO2022070933 A1 WO 2022070933A1
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- sensitive adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/10—Homopolymers or copolymers of unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/10—Homopolymers or copolymers of unsaturated ethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
Definitions
- the present invention relates to a pressure-sensitive adhesive composition and a laminated film using the pressure-sensitive adhesive composition.
- the protective film is a laminate composed of a transparent base material such as polyethylene, polyester, polypropylene, and an adhesive layer, and is peeled off from the adherend after the purpose as the protective film is achieved.
- the protective film When the protective film is peeled off from the adherend, it is required that the protective film can be peeled off cleanly with a small force and that no adhesive residue (glue residue) is generated on the surface of the adherend.
- glue residue glue residue
- Protective film is required.
- the surface protective film using the pressure-sensitive adhesive composition described in Patent Document 1 has a problem that the peeling performance is not sufficient because the pressure-sensitive adhesive force adjusting effect of the pressure-sensitive adhesive composition is insufficient. Further, the pressure-sensitive adhesive composition described in Patent Document 1 contains a compound having a fluorinated alkyl group having 6 carbon atoms, and the compound is a compound of concern for environmental accumulation.
- An object to be solved by the present invention is to provide a pressure-sensitive adhesive composition having an excellent adhesive strength adjusting effect, and a laminated film using the pressure-sensitive adhesive layer as a surface protective film.
- the present invention relates to a pressure-sensitive adhesive composition containing a perfluoropolyether compound (A) having a poly (perfluoroalkylene ether) chain (a1) and a pressure-sensitive adhesive (B).
- (meth) acrylate means one or both of acrylate and methacrylate.
- the pressure-sensitive adhesive composition of the present invention contains a perfluoropolyether compound (A) having a poly (perfluoroalkylene ether) chain (a1) and a pressure-sensitive adhesive (B).
- the perfluoropolyether compound (A) can function as an adhesive force adjusting agent, and by using the adhesive composition of the present invention, a laminated film having excellent peeling performance can be produced.
- each component contained in the pressure-sensitive adhesive composition of the present invention will be described.
- the perfluoropolyether compound (A) has a poly (perfluoroalkylene ether) chain (a1).
- the poly (perfluoroalkylene ether) chain (a1) contained in the compound (A) may have a structure in which divalent fluorinated hydrocarbon groups and oxygen atoms are alternately linked, and is represented by the following general formula (a1-1). The groups represented are mentioned.
- X is a perfluoroalkylene group independently of each other.
- n1 is the number of repetitions.
- two or more kinds of perfluoroalkylene groups may be present randomly or in a block shape.
- Examples of the perfluoroalkylene group of X include the following perfluoroalkylene groups (X-1) to (X-6).
- 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, including the point that it is easily obtained industrially. More preferably, a perfluoromethylene group and a perfluoroethylene group coexist.
- the abundance ratio (X-1 / X-2) (number ratio) is 1/10 to 10 /. 1 is preferable, and 3/10 to 10/3 is more preferable.
- 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, and even more preferably a range of 6 to 70. It is an integer of, 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, and more preferably in the range of 1 to 70%. It is in the range of% by mass.
- the content ratio of the poly (perfluoroalkylene ether) chain (a1) can be calculated and adjusted from the 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).
- the adhesive force adjusting function can be enhanced.
- the polyoxyalkylene chain (a2) contained in the compound (A) may be one in which a plurality of alkylene chains having 1 to 6 carbon atoms such as polyoxyethylene, polyoxypropylene, and polyoxybutylene are linked by an ether bond.
- the structure of the alkylene chain may be linear or branched.
- Examples of the polyoxyalkylene chain (a2) contained in the compound (A) include a group represented by the following formula (a2-1).
- the plurality of Ra 2s are independently alkylene groups having 1 to 6 carbon atoms. n2 is the number of repetitions. )
- two or more kinds of alkylene groups may be present at random or in a block form.
- the polyoxyalkylene chain (a2) is preferably a polyoxyethylene chain and / or a polyoxypropylene chain, and more preferably a polyoxyethylene chain.
- the polyoxyalkylene chain (a2) consists of a polyoxyethylene chain and a polyoxypropylene chain
- the polyoxyethylene chain and the polyoxypropylene chain in the polyoxyalkylene chain (a2) may be present at random and may be blocked. It may exist in the form.
- 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 even more preferably a range of 3 to 50. Is an integer of.
- the content ratio of the polyoxyalkylene chain (a2) of the compound (A) is, for example, in the range of 1 to 90% by mass, preferably in the range of 1 to 80% by mass, and more preferably in the range of 1 to 70% by mass. Is.
- the content ratio of the polyoxyalkylene chain (a2) can be calculated and adjusted from the amount of the polymerizable monomer having the polyoxyalkylene chain (a2) described later.
- Examples of the silicone chain (a3) contained in the compound (A) include a group represented by the following formula (a3-1).
- Each of the plurality of Ra3s is independently an alkyl group or a phenyl group having 1 to 18 carbon atoms.
- n3 is the number of repetitions.
- the alkyl group having 1 to 18 carbon atoms of R a3 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 and n.
- -Butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like can be mentioned.
- the alkyl group having 1 to 18 carbon atoms of Ra3 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.
- 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 ratio of the silicone chain (a3) 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 (a3) can be calculated and adjusted from the amount of the polymerizable monomer having the silicone chain (a3) described later.
- the compound (A) preferably has a polymerizable monomer having a poly (perfluoroalkylene ether) chain (a1), a polymerizable monomer having a polyoxyalkylene chain (a2), and a silicone chain (a3). It is a copolymer containing at least one selected from the group consisting of polymerizable monomers as a polymerization component.
- the "polymerization component” means a component that constitutes a copolymer, and does not include a solvent that does not form a copolymer, a polymerization initiator, or the like.
- the "polymerizable monomer” means a compound having a polymerizable unsaturated group, and the polymerizable unsaturated group includes (meth) acryloyl group, (meth) acryloyloxy group, and (meth).
- C C-containing groups such as acryloylamide group, vinyl ether group, allyl group, styryl group and maleimide group are mentioned, 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 a polymerizable unsaturated group at both ends of the poly (perfluoroalkylene ether) chain, and more preferably poly (perfluoroalkylene ether).
- the molecular weight of the polymerizable monomer having the poly (perfluoroalkylene ether) chain (a1) is, for example, in the range of 300 to 50,000, preferably in the range of 300 to 30,000, and more preferably in the range of 300 to 30,000. It is in the range of 10,000.
- 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).
- the PFPE in the 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.
- a method of reacting and introducing 2-hydroxyethyl (meth) acrylate with a compound having one isocyanate group at each end of the chain, and a method of reacting with 2-hydroxyethyl (meth) acrylamide can be mentioned.
- a method obtained by dehydrochlorating (meth) acrylic acid chloride with a compound having one hydroxyl group at each end of a poly (perfluoroalkylene ether) chain, (meth) acrylic acid anhydride is particularly preferable in that it can be easily obtained synthetically.
- 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).
- R a21 , Ra 22 and Ra 23 are independently alkylene groups having 1 to 6 carbon atoms.
- R a24 is independently a hydrogen atom or a methyl group, respectively.
- Ra25 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- p, q and r are each independently an integer of 0 or more, and p + q + r is an integer of 1 or more.
- the alkylene group having 1 to 6 carbon atoms of R a21 , Ra 22 and Ra 23 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 even more preferably an integer in the range of 3 to 50. be.
- the molecular weight of the polymerizable monomer having the 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. be.
- the polymerizable monomer having a polyoxyalkylene chain (a2).
- Blemmer PE-90, Blemmer PE-200, and Blemmer PE which are hydroxyl group-terminated polyalkylene glycol mono (meth) acrylates, can be used.
- Blemmer APT Series Blemmer 10PPB-500B, Blemmer 10APB-500B (all manufactured by Nichiyu Co., Ltd.); 400, Blemmer PME-1000, Blemmer PME-4000, Blemmer AME-400, Blemmer 50 POEP-800B, Blemmer 50AOEP-800B, Blemmer PLE-200, Blemmer ALE-200, Blemmer ALE-800, Blemmer PSE-400, Blemmer PSE- 1300, Blemmer ASEP series, Blemmer PKEP series, Blemmer AKEP series, Blemmer ANE-300, Blemmer ANE-1300, Blemmer PNEP series, Blemmer PNPE series, Brenmer 43ANEP-500, Brenmer 70ANEP-550 (all manufactured by Nichiyu Co., Ltd.) , Light Acrylate MC, Light Acrylate 130MA, Light Acrylate 041MA, Light Acrylate BO-A, Light Acrylate EC-A
- the polymerizable monomer having a polyoxyalkylene chain (a2) used as a polymerization component may be used alone or in combination of two or more.
- the polymerizable monomer containing the silicone chain (a3) is preferably a compound represented by the following formula (A3-1).
- R a31 is independently an alkyl group having 1 to 6 carbon atoms or a group represented by —OSI ( Ra34 ) 3 (R a34 is an independently 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 and 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 repetitions.
- 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 having 1 to 50 carbon atoms of L 1 is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and further preferably a methylene group or ethylene. Group, n-propylene group or isopropylene group.
- the alkyleneoxy group having 1 to 50 carbon atoms of L 1 is, for example, a group in which one of the alkylene groups having 1 to 50 carbon atoms is substituted with —O—.
- the alkyleneoxy group having 1 to 50 carbon atoms of L1 is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and further preferably methylene. It is an oxy 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.
- the carbon atoms constituting the alkylene group having 1 to 50 carbon atoms and the alkyleneoxy group having 1 to 50 carbon atoms of L1 are substituted with one or more substituents such as a hydroxyl group, a phenyl group and a phenoxy group. good.
- m is an integer of 1 to 6 independently.
- n3 is the number of repetitions, for example, in the range of 1 to 200, preferably in the range of 1 to 150.
- Ra 32 is an alkyl group having 1 to 6 carbon atoms independently.
- R a33 is an alkyl group having 1 to 6 carbon atoms independently.
- R a35 is a hydrogen atom or a methyl group independently of each other.
- 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. be.
- the polymerizable monomer containing the silicone chain (a3) used as the polymerization component may be used alone or in combination of two or more.
- the compound (A) is a polymerizable monomer having a poly (perfluoroalkylene ether) chain (a1), a polymerizable monomer having a polyoxyalkylene chain (a2), and a polymerizable single having a silicone chain (a3).
- Other polymerizable monomers other than the weight may be used as the polymerization component.
- Examples of the other polymerizable monomer include a polymerizable monomer having an alkyl group (a4) having 1 to 18 carbon atoms and a polymerizable unit having an aromatic group (a5) having 6 to 18 carbon atoms.
- the body etc. can be mentioned.
- the alkyl group (a4) having 1 to 18 carbon atoms may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group and n.
- -Butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like can be mentioned.
- the alkyl group (a4) having 1 to 18 carbon atoms may be substituted with one or more substituents such as a hydroxyl group, a phenyl group and a phenoxy group.
- the alkyl group (a4) having 1 to 18 carbon atoms includes, for example, a hydroxyalkyl group having 1 to 18 carbon atoms, a phenylalkyl group having 7 to 18 carbon atoms, and a phenoxyalkyl group having 7 to 18 carbon atoms.
- Examples of the aromatic group (a5) having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, an anthracene-1-yl group, and a phenanthrene-1-yl group.
- the aromatic group (a5) having 6 to 18 carbon atoms may be further substituted with a substituent such as a hydroxyl group, an alkyl group or an alkoxy, for example, a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms. include.
- Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and the polymerizable unsaturated group being a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl.
- Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and the polymerizable unsaturated group being a vinyl ether group include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, and n-butyl vinyl ether.
- Alkyl vinyl ethers such as 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, cycloalkyl vinyl ether, 2-hydroxyethyl vinyl ether.
- Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and having a polymerizable unsaturated group as an allyl group include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether. And so on.
- Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and the polymerizable unsaturated group being a (meth) acryloylamide group include N, N-dimethylacrylamide, N, N-diacetoneacrylamide, and the like. Examples thereof include N-isopropylacrylamide, diacetoneacrylamide, acroylmorpholin and the like.
- Examples of the polymerizable monomer having an alkyl group having 1 to 18 carbon atoms and the polymerizable unsaturated group being a maleimide group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, and octylmaleimide. Examples thereof include dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.
- Examples of the polymerizable monomer having a hydroxyalkyl group having 1 to 18 carbon atoms and the polymerizable unsaturated group being a (meth) acryloyl group include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). Examples thereof include 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 having a polymerizable unsaturated group as a (meth) acryloyl group include benzyl (meth). ) Acrylate, 2-phenoxymethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like.
- Examples of the polymerizable monomer having an aromatic group having 6 to 18 carbon atoms include styrene, ⁇ -methylstyrene, p-methylstyrene, p-methoxystyrene and the like.
- the other monomer used as a polymerization component may be used alone or in combination of two or more.
- the compound (A) is a polymerizable unit other than the polymerizable monomer having a poly (perfluoroalkylene ether) chain (a1) and the polymerizable monomer having a poly (perfluoroalkylene ether) chain (a1).
- a copolymer containing a polymer (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.
- the copolymer may be, for example, any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer and the like.
- the charging ratio of each of the above-mentioned polymerizable monomers is not particularly limited.
- the amount of the polymerizable monomer having the poly (perfluoroalkylene ether) chain (a1) is, for example, in the range of 1 to 90% by mass, preferably in the range of 1 to 80% by mass, and more. It is preferably in the range of 1 to 70% by mass.
- the compound (A) is polymerizable including a polymerizable monomer having a poly (perfluoroalkylene ether) chain (a1), a polymerizable monomer containing a polyoxyalkylene chain (a2), and a silicone chain (a3).
- a copolymer containing one or more selected from the group consisting of monomers as a polymerization component with respect to 100 parts by mass of the polymerizable monomer having a poly (perfluoroalkylene ether) chain (a1).
- the total of the polymerizable monomer containing the polyoxyalkylene chain (a2) and the polymerizable monomer containing the silicone chain (a3) is, for example, in the range of 5 to 2,000 parts by mass, preferably 10 to 2, It is in the range of 000 parts by mass, more preferably in the range of 15 to 2,000 parts by mass.
- the compound (A) is preferably a polymer containing a poly (perfluoroalkylene ether) chain (a1) in the main chain and a polyoxyalkylene chain (a2) and / or a silicone chain (a3) in the side chain.
- the "main chain” means the longest molecular chain among the molecular chains constituting the compound (A)
- the "side chain” means a molecular chain other than the main chain.
- the compound (A) preferably contains a polymerizable monomer having a polymerizable unsaturated group at both ends of the poly (perfluoroalkylene ether) chain (a1) and a polyoxyalkylene chain (a2). It is a copolymer containing at least one selected from the group consisting of a polymer and a polymerizable monomer containing a silicone chain (a3) as a polymerization component.
- Compound (A) preferably does not have a perfluoroalkyl group having 6 or more carbon atoms. Since the compound (A) does not contain a perfluoroalkyl group having 6 or more carbon atoms, the environmental load can be reduced. Here, the "perfluoroalkyl group having 6 or more carbon atoms" does not include a poly (perfluoroalkylene ether) chain.
- Compound (A) preferably does not have an alkyl fluorinated group. Since the compound (A) does not have a fluorinated alkyl group, compatibility with the base resin can be ensured.
- the weight average molecular weight of the compound (A) is not particularly limited, but from the viewpoint of compatibility with the adhesive (B) described later, ease of adjusting the adhesive force, and reduction of adhesive residue, etc., 3 It is preferably in the range of 000 to 300,000, more preferably in the range of 3,000 to 200,000, and more preferably in the range of 4,000 to 100,000 for large-area optical members and the like. It is most preferable from the viewpoint of uniformity of peeling force when used as a surface protective film.
- 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 the compound (A) can be produced by a known method.
- 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 anion polymerization method, but the radical polymerization method is particularly convenient.
- Industrially preferred the polymerizable monomer mixture can be produced by adding a general-purpose radical polymerization initiator in an organic solvent and polymerizing the mixture.
- a dropping polymerization method in which the polymer monomer and the initiator are dropped into a reaction vessel according to the polymerizable monomer used is also effective for obtaining a copolymer having a uniform composition.
- polymerization initiator various substances can be used, for example, peroxides such as benzoyl peroxide and diacyl peroxide, azobisisobutyronitrile, dimethyl azobisisobutyrate, phenylazotriphenylmethane and the like.
- peroxides such as benzoyl peroxide and diacyl peroxide, azobisisobutyronitrile, dimethyl azobisisobutyrate, phenylazotriphenylmethane and the like.
- peroxides such as benzoyl peroxide and diacyl peroxide
- azobisisobutyronitrile dimethyl azobisisobutyrate
- phenylazotriphenylmethane phenylazotriphenylmethane
- transition metal catalyst that causes living radical polymerization.
- a chain transfer agent such as lauryl mercaptoethanol, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, or a thiol compound having a coupling group such as ⁇ -mercaptopropyltrimethoxysilane can be used as a chain transfer agent. It may be used as an additive of.
- the polymerization can be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent from the viewpoint of workability.
- a solvent used for the 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, methyl acetate and acetic acid.
- Ethers such as ethyl, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, 2-methoxypropion Monocarboxylic acid esters such as methyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, methylcellosolve, cellosolve , Ethers such as butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol
- 1,1,1-Trichloroethane 1,1,1-Trichloroethane, halogen-based solvents such as chloroform, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene and xylene, and perfluorooctane, perfluorotri-n-butylamine and the like. Examples include fluorinated inert liquids. These solvents may be used alone or in combination of two or more.
- the solvent used for the polymerization of compound (A) may be the solvent of the pressure-sensitive adhesive composition of the present invention.
- the adhesive (B) can be used without particular limitation as long as it has adhesiveness.
- an acrylic adhesive, a urethane adhesive, a synthetic rubber adhesive, a natural rubber adhesive, and a silicone adhesive are preferable to use.
- 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.
- the (meth) acrylic monomer may be used as a main component of one kind or two or more kinds.
- the "main component” in the present invention means the most abundant component in the total amount of the constituent components, and the "main component” preferably exceeds 40% by mass, more preferably exceeds 50% by mass, and is further preferable. Means that it exceeds 60% by 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, and s-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)
- examples thereof include acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate.
- (meth) acrylic monomers hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, and isononyl (meth).
- Alkyl having 6 to 14 carbon atoms such as acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate.
- the (meth) acrylic monomer having a group is preferable from the viewpoint that the adhesive force to the adherend can be easily controlled to be low and the removability is excellent.
- 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.
- a (meth) acrylic monomer having a hydroxyl group one kind or two or more kinds can be used.
- the (meth) acrylic monomer having a hydroxyl group By using the (meth) acrylic monomer having a hydroxyl group, it becomes easy to control cross-linking of the pressure-sensitive adhesive composition, and by extension, it becomes easy to control the balance between the improvement of wettability by flow and the reduction of adhesive force in peeling. Also, it is 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, and 6-hydroxyhexyl (meth).
- it is preferable to use a (meth) acrylic monomer having a hydroxyl group having 4 or more carbon atoms in the alkyl group because light peeling at the time of high-speed peeling becomes easy.
- the (meth) acrylic monomer having a hydroxyl group is contained in an amount of 15 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms. It is preferably 1 to 13 parts by mass, more preferably 2 to 10 parts by mass, and most preferably 3 to 8 parts by mass. When it is within the above range, it is easy to control the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive force of the obtained pressure-sensitive adhesive layer, which is preferable.
- the Tg is set to 0 ° C or lower (usually -100 ° C or higher) because it is easy to balance the adhesive performance, and the glass transition temperature and peelability of the (meth) acrylic polymer are adjusted.
- a polymerizable monomer or the like for adjusting can be used.
- (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 a hydroxyl group.
- Examples of the (meth) acrylic monomer having a carboxyl group include (meth) acrylic acid, carboxylethyl (meth) acrylate, and carboxylpentyl (meth) acrylate.
- the (meth) acrylic monomer having a carboxyl group is preferably 5 parts by mass or less with respect to 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 or equal to parts by mass, further preferably less than 1 part by mass, even more preferably less than 0.2 parts by mass, and most preferably 0.01 parts by mass or more and less than 0.1 parts by mass. Within the above range, it is possible to prevent the adhesive strength from increasing with time (adhesive strength increase preventing property), which is preferable.
- the polymerizable monomer other than the acrylic monomer can be used without particular limitation.
- a cohesiveness / heat resistance improving component such as a cyano group-containing monomer, a vinyl ester monomer, and an aromatic vinyl monomer, an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, and N-acryloylmorpholin.
- a component having a functional group that acts as a base point for improving adhesive strength and cross-linking such as a vinyl ether monomer
- a vinyl ether monomer can be appropriately used.
- 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.
- nitrogen-containing monomer it is possible to secure an appropriate adhesive force that does not cause floating or peeling, and it is possible to obtain a surface protective film having excellent shearing force, which is useful.
- 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.
- vinyl ester monomer examples include vinyl acetate, vinyl propionate, vinyl laurate and the like.
- aromatic vinyl monomer examples include styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, and other substituted styrenes.
- amide group-containing monomer examples include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethyl.
- examples thereof include methacrylamide, N, N'-methylenebisacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide, diacetoneacrylamide and the like.
- Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
- amino group-containing monomer examples include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and the like.
- epoxy group-containing monomer examples include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
- vinyl ether monomer examples include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and the like.
- the (meth) acrylic polymer may further contain a polyoxyalkylene chain-containing reactive monomer as a monomer component.
- the average c of the oxyalkylene units of the polyoxyalkylene group-containing reactive monomer is preferably 1 to 40, more preferably 3 to 40, still more preferably 4 to 35, and 5 to 35. 30 is particularly preferable.
- the average number of added moles is 1 or more, the effect of reducing contamination of the adherend (protected body) tends to be efficiently obtained. Further, when the average number of added moles is larger than 40, the viscosity of the pressure-sensitive adhesive composition tends to increase, making coating difficult.
- the terminal of the oxyalkylene chain may remain 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 two or more, but the total content is the monomer component of the (meth) acrylic polymer. It is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 4% by mass or less, and 3% by mass or less in the total amount. Is particularly preferable, and it is still more preferable that the content is 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, for example, an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group and the like. Can be mentioned.
- the hydrocarbon group of the oxyalkylene chain may be linear or branched.
- the polyoxyalkylene chain-containing reactive monomer is a reactive monomer having an ethylene oxide group.
- a (meth) acrylic polymer having a reactive monomer having an ethylene oxide group as a base polymer, the compatibility between the base polymer and the perfluoropolyether compound (A) is improved, and bleeding to an adherend is preferable. It is easy to obtain a low-staining pressure-sensitive adhesive composition.
- polyoxyalkylene chain-containing reactive monomer examples include a (meth) acrylic acid alkylene oxide adduct, a reactive surfactant having a reactive substituent such as an acryloyl group, a methacryloyl group, and an allyl group in the molecule. Can be mentioned.
- (meth) acrylic acid alkylene oxide adduct examples include polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, and polyethylene glycol-polybutylene glycol (meth).
- the reactive surfactant include, for example, an anionic reactive surfactant having a (meth) acryloyl group or an allylic group, a nonionic reactive surfactant, a cationic reactive surfactant, and the like. Can be mentioned.
- the (meth) acrylic polymer constituting the acrylic pressure-sensitive adhesive (b1) preferably has a weight average molecular weight (Mw) of 100,000 to 5 million, more preferably 200,000 to 2 million, and further preferably 300,000 to 300,000. It is 800,000.
- Mw weight average molecular weight
- the weight average molecular weight is larger than 100,000, the cohesive force of the pressure-sensitive adhesive layer becomes appropriate and the adhesive residue tends to be suppressed.
- the weight average molecular weight is 5 million or less, the fluidity of the polymer is appropriate, the adherend is sufficiently wetted, and blisters generated between the adherend and the pressure-sensitive adhesive layer of the surface protective film are generated. Can be suppressed.
- the weight average molecular weight is 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).
- Tg glass transition temperature
- the glass transition temperature of the (meth) acrylic polymer can be adjusted within the above range by appropriately changing the monomer component and the composition ratio to be used.
- the polymerization method of the (meth) acrylic polymer is not particularly limited and can be polymerized by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc., but in particular from the viewpoint of workability and subject matter.
- Solution polymerization is a more preferable embodiment from the viewpoint of characteristics such as low contamination of the body (protected body).
- the obtained polymer may be any of a random copolymer, a block copolymer, an alternate copolymer, a graft copolymer and the like.
- the urethane-based pressure-sensitive adhesive (b2) preferably includes a urethane resin (urethane-based polymer) obtained by reacting a polyol with a polyisocyanate compound.
- a urethane resin urethane-based polymer obtained by reacting a polyol with a polyisocyanate compound.
- the polyol include polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols and the like.
- the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate.
- any suitable silicone-based pressure-sensitive adhesive can be adopted.
- a silicone-based pressure-sensitive adhesive preferably, one obtained by blending or aggregating a silicone resin (silicone-based polymer, silicone component) can be adopted.
- silicone-based adhesive examples include an addition reaction-curable silicone-based adhesive and a peroxide-curable silicone-based adhesive.
- addition reaction-curable silicone-based pressure-sensitive adhesives are preferable because they do not use peroxides (benzoyl peroxide or the like) and do not generate decomposition products.
- the blending ratio of the perfluoropolyether compound (A) and the pressure-sensitive adhesive (B) may be appropriately set according to the desired adhesive strength.
- the content of the perfluoropolyether compound (A) is 0.01 to 20% by mass in the solid content of the pressure-sensitive adhesive composition. Is preferable, and 0.1 to 5.0% by mass is more preferable. Within this range, the perfluoropolyether compound (A) can sufficiently exert its function as an adhesive strength adjusting agent.
- the "solid content” means a component obtained by removing the solvent from the pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive composition of the present invention may contain the perfluoropolyether compound (A) and the pressure-sensitive adhesive (B), and optionally contains other components such as various additives as long as the effects of the present invention are not impaired. be able to.
- the pressure-sensitive adhesive composition of the present invention preferably contains a cross-linking agent as another component.
- a cross-linking agent 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 containing a cross-linking agent, the constituent unit and the constituent ratio of the (meth) acrylic polymer are contained.
- the cross-linking agent By appropriately adjusting the selection of the cross-linking agent, the addition ratio, and the like for cross-linking, a pressure-sensitive adhesive layer having higher heat resistance can be easily obtained.
- an isocyanate compound an epoxy compound, a melamine-based resin, an aziridine derivative, a metal chelate compound and the like may be used, and the use of an isocyanate compound is particularly preferable. Further, these compounds may be used alone or in combination of two or more.
- isocyanate compound examples include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI) and dimerate diisocyanate, and fats such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate (IPDI).
- aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI) and dimerate diisocyanate
- fats such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate (IPDI).
- Aromatic isocyanates such as ring group isocyanates, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate (XDI), these isocyanate compounds are allophanate bond, biuret bond, isocyanurate bond, uretdione bond. , Urea bond, carbodiimide bond, uretonimine bond, oxadiazine trione bond and the like, and examples thereof include polyisocyanate modified products.
- Examples of commercially available products of the isocyanate compound include trade names Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (all manufactured by Takeda Pharmaceutical Company Limited), Sumijour T80, Sumijuru L, and Death Module N3400 (or more). , Sumika Bayer Urethane Co., Ltd.), Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (all manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like. These isocyanate compounds may be used alone or in combination of two or more, or a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound may be used in combination. By using a mixture of two or more cross-linking agents, it is possible to achieve both adhesiveness and resilience resistance (adhesiveness to curved surfaces), and it is possible to obtain a laminated film having more excellent adhesive reliability.
- epoxy compound examples include N, N, N', N'-tetraglycidyl-m-xylene diamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Company, Inc.) and 1,3-bis (N, N-diamine).
- examples thereof include glycidylaminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Company, Inc.).
- Examples of the melamine resin include hexamethylol melamine and the like.
- Examples of the aziridine derivative include commercial products such as HDU, TAZM, and TAZO (all manufactured by Mutual Pharmaceutical Co., Ltd.).
- metal chelate compound examples include aluminum, iron, tin, titanium, nickel and the like as metal components, and acetylene, methyl acetoacetate, ethyl lactate and the like as chelate components.
- the content of the cross-linking agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer used in the acrylic pressure-sensitive adhesive (b1), for example. It is more preferably 0.1 to 15 parts by mass, further preferably 0.5 to 10 parts by mass, and most preferably 1.0 to 6 parts by mass.
- the cross-linking agent may be used alone or in combination of two or more.
- the pressure-sensitive adhesive composition can contain a cross-linking catalyst for more effectively advancing any of the above-mentioned cross-linking reactions.
- a cross-linking catalyst for more effectively advancing any of the above-mentioned cross-linking reactions.
- the cross-linking catalyst include tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris (acetylacetonato) iron, tris (hexane-2,4-dionat) iron, and tris (heptane-2,4-dionat).
- the content of the cross-linking catalyst is not particularly limited, but is preferably about 0.0001 to 1 part by mass, and 0.001 to 0.5 part by mass, for example, with respect to 100 parts by mass of the (meth) acrylic polymer. Parts by mass are more preferred.
- the rate of the crosslinking reaction is high when the pressure-sensitive adhesive layer is formed, and the pot life of the pressure-sensitive adhesive composition is long, which is a preferable embodiment.
- the laminated film of the present invention has an adhesive layer and a base material layer, and the adhesive layer is a layer formed by 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 base material layer.
- the laminated film of the present invention can also be produced by transferring a pressure-sensitive adhesive layer obtained by pre-crosslinking the pressure-sensitive adhesive composition of the present invention onto at least one surface of a base material layer.
- the method for forming the pressure-sensitive adhesive layer on the base material layer is not particularly limited.
- the pressure-sensitive adhesive composition (solution) of the present invention is applied to the base material, and the polymerization solvent or the like is dried and removed to form the pressure-sensitive adhesive layer. It is produced by forming on a material. After that, curing may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer, adjusting the cross-linking reaction, and the like.
- the pressure-sensitive adhesive composition is applied onto a base material to prepare a laminated film, one or more solvents other than the polymerization solvent are newly added to the pressure-sensitive adhesive composition so that the pressure-sensitive adhesive composition can be uniformly applied on the base material layer. May be added.
- a known method used for manufacturing pressure-sensitive adhesive tapes is used. Specific examples thereof include a roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, an air knife coat method, an extrusion coat method using a die coater and the like.
- 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 ⁇ m, preferably about 3 to 100 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is within the range, it is easy to obtain an appropriate balance between removability and adhesiveness, which is preferable.
- the laminated film of the present invention preferably has a total thickness of 1 to 400 ⁇ m, more preferably 10 to 200 ⁇ m, and most preferably 20 to 150 ⁇ m.
- the “total thickness” means the total thickness of the laminated film including all layers such as the base material layer, the pressure-sensitive adhesive layer, and the antistatic layer.
- the base material layer constituting the laminated film of the present invention is not particularly limited, but is, for example, transparency, mechanical strength, thermal stability, moisture shielding property, isotropic, flexibility, and dimensional stability. It is preferable to use a base material having excellent properties such as properties.
- the pressure-sensitive adhesive composition can be applied by a roll coater or the like, and can be wound into a roll shape, which is useful.
- polyester polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate; cellulose polymers such as diacetyl cellulose and triacetyl cellulose; polycarbonate polymers.
- An acrylic polymer such as polymethylmethacrylate; a plastic film composed of a resin material containing the main resin component (main component of the resin component, typically a component occupying 50% by mass or more). can.
- the resin material examples include styrene polymers such as polystyrene and acrylonitrile-styrene copolymers; olefin polymers such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; Examples thereof include those using a vinyl chloride polymer; an amide polymer such as nylon 6, nylon 6, 6 and aromatic polyamide; and the like as a resin material.
- the resin material include 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, and vinyl butyral-based polymers. , Arilate-based polymer, polyoxymethylene-based polymer, epoxy-based polymer and the like. It may be a base material composed of two or more kinds of blends of the above-mentioned polymers.
- the base material a plastic film made of a transparent thermoplastic resin material can be preferably adopted.
- the plastic films it is more preferable to use a polyester film.
- the polyester film is mainly composed of 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. say.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- polybutylene terephthalate polybutylene terephthalate.
- Such a polyester film has preferable properties as a base material of a surface protective film, such as excellent optical properties and dimensional stability.
- additives such as antioxidants, ultraviolet absorbers, plasticizers, colorants (pigments, dyes, etc.), antistatic agents, antiblocking agents, etc. are blended in the resin material constituting the base material, if necessary. It may have been done. Further, the surface of the film used as a base material may be subjected to known or conventional surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of an undercoat agent.
- the laminated film of the present invention may have an antistatic layer on the base material layer, and it is also possible to use a plastic film which has been subjected to antistatic treatment as the base material. It is preferable to use such a base material because the charge of the film itself at the time of peeling can be suppressed. Further, the base material is a plastic film, and by applying the antistatic treatment to the plastic film, it is possible to obtain a film in which the charge of the laminated film itself is reduced and the antistatic ability to the adherend is excellent.
- the method for imparting the antistatic function is not particularly limited, and a conventionally known method can be used. For example, an antistatic resin, a conductive polymer, or a conductive substance composed of an antistatic agent and a resin component can be used.
- Examples thereof include a method of applying the contained conductive resin, a method of depositing or plating a conductive substance, and a method of kneading an antistatic agent or the like.
- a lubricant can also be used in combination.
- the thickness of the base material layer is usually about 5 to 200 ⁇ m, preferably about 10 to 100 ⁇ m. When the thickness of the base material layer is within the above range, it is preferable because it is excellent in the workability of attaching to the adherend and the workability of peeling from the adherend.
- a separator can be attached to the surface of the adhesive layer for the purpose of protecting the adhesive surface as needed.
- Paper and plastic film are examples of the material constituting the separator, but the plastic film is preferably used because of its excellent surface smoothness.
- the film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and is, for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride co-weight.
- Examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
- the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 10 to 100 ⁇ m. 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 from the pressure-sensitive adhesive layer.
- the separator may be subjected to mold release and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based mold release agent, silica powder, etc., as needed, as well as a coating type, a kneading type, and a vapor deposition type. It is also possible to perform antistatic treatment such as.
- 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 has excellent stability over time and can be used for surface protection applications such as processing, transportation, and shipping, and is therefore useful for applications of protecting the surface of optical members such as polarizing plates.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene-converted values based on gel permeation chromatography (GPC) measurement.
- GPC gel permeation chromatography
- the reaction was carried out 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 by gas chromatography measurement.
- Each of the plurality of Xs is independently a perfluoromethylene group or a perfluoroethylene group, and each molecule has an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and is a fluorine atom.
- the number of is 46 on average.
- the number average molecular weight by GPC is 1,500.
- Each of the plurality of Xs is independently a perfluoromethylene group or a perfluoroethylene group, and each molecule has an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and is a fluorine atom. The number of is 46 on average.
- the weight average molecular weight Mw was 5,300.
- the fluorine content in the reaction raw material used was 11% by mass.
- the weight average molecular weight Mw was 18,500.
- Example 1 2.9 parts of D-100K (manufactured by DIC) as a curing agent (crosslinking agent) and 2.9 parts of the obtained perfluoropolyether with respect to 100 parts of the solid content of the acrylic pressure-sensitive adhesive (CT-3088: manufactured by DIC).
- CT-3088 manufactured by DIC
- 0.5 part of the compound (A1) was added, diluted with methyl ethyl ketone so that the solid content was 35%, and sufficiently mixed to obtain a pressure-sensitive adhesive composition.
- the obtained pressure-sensitive adhesive composition was applied to the coroner-treated surface of a polyester film having a thickness of 50 ⁇ m as a base material so that the thickness of the pressure-sensitive adhesive layer after formation was 20 ⁇ m. Directly coated using (manufactured by).
- ⁇ Initial adhesive strength evaluation> The obtained laminated film was pressure-bonded to a glass plate with one reciprocation of a 2 kgf roller to be attached as an evaluation sample. Twenty-four hours after the application, the adhesive strength of the evaluation sample was measured using the adhesive / film peeling analyzer VPA-3 (manufactured by Kyowa Interface Science). The measurement conditions are as follows. The adhesive strength was evaluated in two patterns, one in which the tensile speed and the peeling speed were set to 150 mm / min and the other in which the tensile speed and the peeling speed were set to 1,200 mm / min.
- 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.
- the laminated film using the pressure-sensitive adhesive composition containing the perfluoropolyether compound (A1) is laminated using the pressure-sensitive adhesive composition containing the perfluoroalkyl group-containing compound (A'1). It was found that the peeling performance was superior to that of the film (Comparative Example 1) and the laminated film (Comparative Example 2) using the pressure-sensitive adhesive composition containing no pressure-sensitive adhesive. Since the perfluoroalkyl group-containing compound (A'1) is a compound having a perfluorohexyl group, it is a compound of concern for environmental accumulation.
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Abstract
Description
上記保護フィルムは、ポリエチレン、ポリエステル、ポリプロピレン等の透明な基材と粘着剤層からなる積層体であり、保護フィルムとしての目的が果たされた後は、被着体から剥離される。
近年大型化するディスプレイに用いられる光学部材に対しては、機械による表面保護フィルムの剥離が主流となっており、剥離スピードが工程によって異なることも多く、より剥離性が良好で、糊残りの少ない保護フィルムが求められている。
尚、本願明細書において、「(メタ)アクリレート」とは、アクリレートとメタクリレートの一方又は両方をいう。
本発明の粘着剤組成物は、ポリ(パーフルオロアルキレンエーテル)鎖(a1)を有するパーフルオロポリエーテル化合物(A)と、粘着剤(B)とを含有する。
パーフルオロポリエーテル化合物(A)は、粘着力調整剤として機能することができ、本発明の粘着剤組成物を用いることで剥離性能に優れる積層フィルムを製造することができる。
以下、本発明の粘着剤組成物が含有する各成分について説明する。
パーフルオロポリエーテル化合物(A)は、ポリ(パーフルオロアルキレンエーテル)鎖(a1)を有する。
化合物(A)が有するポリ(パーフルオロアルキレンエーテル)鎖(a1)は、2価のフッ化炭化水素基と酸素原子が交互に連結した構造であればよく、下記一般式(a1-1)で表される基が挙げられる。
前記パーフルオロメチレン基(X-1)とパーフルオロエチレン基(X-2)とが共存する場合、その存在比(X-1/X-2)(個数の比)は1/10~10/1が好ましく、3/10~10/3がより好ましい。
ポリ(パーフルオロアルキレンエーテル)鎖(a1)の含有割合は、後述するポリ(パーフルオロアルキレンエーテル)鎖(a1)を有する重合性単量体の仕込み量より算出及び調整できる。
ポリオキシアルキレン鎖(a2)がポリオキシエチレン鎖及びポリオキシプロピレン鎖からなる場合、ポリオキシアルキレン鎖(a2)中のポリオキシエチレン鎖及びポリオキシプロピレン鎖は、ランダムに存在してもよく、ブロック状に存在してもよい。
ポリオキシアルキレン鎖(a2)の含有割合は、後述するポリオキシアルキレン鎖(a2)を有する重合性単量体の仕込み量より算出及び調整できる。
Ra3の炭素原子数1~18のアルキル基は、好ましくは炭素原子数1~6のアルキル基であり、より好ましくはメチル基である。
シリコーン鎖(a3)の含有割合は、後述するシリコーン鎖(a3)を有する重合性単量体の仕込み量より算出及び調整できる。
ここで「重合成分」とは、共重合体を構成する成分という意味であり、共重合体を構成しない溶媒や重合開始剤等は含まれない。
これらのなかでも、ポリ(パーフルオロアルキレンエーテル)鎖の両末端に水酸基を1つずつ有する化合物に対して、(メタ)アクリル酸クロライドを脱塩酸反応させて得る方法、(メタ)アクリル酸無水物を反応させて得る方法、又は2-(メタ)アクリロイルオキシエチルイソシアネートをウレタン化反応させて得る方法が合成上得られやすい点で特に好ましい。
Ra21、Ra22及びRa23は、それぞれ独立に、炭素原子数1~6のアルキレン基であり、
Ra24は、それぞれ独立に、水素原子またはメチル基であり、
Ra25は、水素原子又は炭素原子数1~6のアルキル基であり、
p、q及びrは、それぞれ独立に、0以上の整数であり、p+q+rは1以上の整数である。)
Ra31は、それぞれ独立に、炭素原子数1~6のアルキル基又は-OSi(Ra34)3で表される基(Ra34はそれぞれ独立に炭素原子数1~3のアルキル基)であり、
Ra32及びRa33は、それぞれ独立に、炭素原子数1~6のアルキル基であり、
Ra35は、水素原子又はメチル基であり、
L1は、炭素原子数1~50のアルキレン基又は炭素原子数1~50のアルキレンオキシ基であり、
n3は繰り返し数である。)
Ra33は、好ましくはブチル基である。
n3の繰り返し数は、例えば1~200の範囲であり、好ましくは1~150の範囲である。
L1の炭素原子数1~50のアルキレンオキシ基は、好ましくは炭素原子数1~15のアルキレンオキシ基であり、より好ましくは炭素原子数1~8のアルキレンオキシ基であり、さらに好ましくはメチレンオキシ基、エチレンオキシ基、プロピレンオキシ基、オキシトリメチレン基、ブチレンオキシ基、オキシテトラメチレン基、ペンチレンオキシ基、ヘプチレンオキシ基又はオクチレンオキシ基である。
mは、それぞれ独立に、1~6の整数である。
n3は、繰り返し数であり、例えば1~200の範囲であり、好ましくは1~150の範囲である。
Ra32は、それぞれ独立に、炭素原子数1~6のアルキル基である。
Ra33は、それぞれ独立に、炭素原子数1~6のアルキル基である。
Ra35は、それぞれ独立に、水素原子又はメチル基である。)
炭素原子数1~18のアルキル基(a4)は、例えば炭素原子数1~18のヒドロキシアルキル基、炭素原子数7~18のフェニルアルキル基、炭素原子数7~18のフェノキシアルキル基を含む。
炭素原子数6~18の芳香族基(a5)は、さらに水酸基、アルキル基、アルコキシ等の置換基が置換していてもよく、例えば炭素原子数1~6のアルキル基が置換したフェニル基を含む。
上記共重合体は、例えばランダム共重合体、ブロック共重合体、交互共重合体、グラフト共重合体等のいずれでもよい。
ポリ(パーフルオロアルキレンエーテル)鎖(a1)を有する重合性単量体の量は、重合成分全体の例えば1~90質量%の範囲であり、好ましくは1~80質量%の範囲であり、より好ましくは1~70質量%の範囲である。
ここで「主鎖」とは、化合物(A)を構成する分子鎖のうち最も長い分子鎖を意味し、「側鎖」とは主鎖以外の分子鎖を意味する。
化合物(A)が、炭素原子数が6以上のパーフルオロアルキル基を含まないことで、環境負荷を低減することができる。
尚、ここで「炭素原子数が6以上のパーフルオロアルキル基」とは、ポリ(パーフルオロアルキレンエーテル)鎖は含まない。
化合物(A)をフッ素化アルキル基を有さないことで、ベース樹脂への相溶性が担保できる。
本発明における重量平均分子量は、実施例に記載の方法により測定して得られる値である。
化合物(A)は、ラジカル重合法、カチオン重合法、アニオン重合法等の重合機構に基づき、溶液重合法、塊状重合法、エマルジョン重合法等により製造できるが、特にラジカル重合法が簡便であり、工業的に好ましい。例えば、重合性単量体混合物を有機溶媒中、汎用のラジカル重合開始剤を添加し、重合させることにより製造できる。
用いる重合性単量体に応じて、反応容器に重合体単量体と開始剤とを滴下しながら重合する滴下重合法等も、均一な組成の共重合体を得るために有効である。
必要に応じて、ラウリルメルカプタン、2-メルカプトエタノール、エチルチオグリコール酸、オクチルチオグリコール酸等の連鎖移動剤や、γ-メルカプトプロピルトリメトキシシラン等のカップリング基を有するチオール化合物を連鎖移動剤等の添加剤として用いてもよい。
重合に用いる溶剤としては、例えば、エタノール、イソプロピルアルコール、n-ブタノール、iso-ブタノール、tert-ブタノール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン等のケトン類、酢酸メチル、酢酸エチル、酢酸ブチル、乳酸メチル、乳酸エチル、乳酸ブチル等のエステル類、2-オキシプロピオン酸メチル、2-オキシプロピオン酸エチル、2-オキシプロピオン酸プロピル、2-オキシプロピオン酸ブチル、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチル、2-メトキシプロピオン酸プロピル、2-メトキシプロピオン酸ブチル等のモノカルボン酸エステル類、ジメチルホルムアミド、ジメチルスルホキシド、N-メチルピロリドン等の極性溶剤、メチルセロソルブ、セロソルブ、ブチルセロソルブ、ブチルカルビトール、エチルセロソルブアセテート等のエーテル類、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等のプロピレングリコール類およびそのエステル類、1,1,1-トリクロルエタン、クロロホルム等のハロゲン系溶剤、テトラヒドロフラン、ジオキサン等のエーテル類、ベンゼン、トルエン、キシレン等の芳香族類、更にパーフルオロオクタン、パーフルオロトリ-n-ブチルアミン等のフッ素化イナートリキッド類等が挙げられる。
これら溶剤は、1種単独で用いることも2種以上併用することもできる。
化合物(A)の重合に用いる溶剤は、本発明の粘着剤組成物の溶剤としてよい。
粘着剤(B)としては、粘着性を有するものであれば特に制限なく使用でき、例えば、アクリル系粘着剤、ウレタン系粘着剤、合成ゴム系粘着剤、天然ゴム系粘着剤、シリコーン系粘着剤等が挙げられる。これら粘着剤のなかでも、アクリル系粘着剤(b1)および/またはウレタン系粘着剤(b2)を用いることが好ましい。
前記(メタ)アクリル系モノマーは、1種または2種以上を主成分として使用することができる。前記炭素原子数が1~14のアルキル基を有する(メタ)アクリル系モノマーを用いることにより、被着体(被保護体)に対する粘着力を低く制御することが容易となり、軽剥離性や再剥離性に優れた表面保護フィルムが得られる。
尚、本発明における「主成分」とは、構成する成分全量中において最も多い成分を意味し、当該「主成分」が好ましくは40質量%を超え、より好ましくは50質量%を超え、さらに好ましくは60質量%を超えることをいう。
前記平均付加モル数が1以上の場合、被着体(被保護体)の汚染低減効果が効率よく得られる傾向がある。また、前記平均付加モル数が40より大きい場合、粘着剤組成物の粘度が上昇して塗工が困難となる傾向がある。なお、オキシアルキレン鎖の末端は、ヒドロキシル基のままや、他の官能基等で置換されていてもよい。
尚、前記重量平均分子量は、GPC(ゲル・パーミエーション・クロマトグラフィー)により測定して得られたものをいう。
尚、(メタ)アクリル系ポリマーのガラス転移温度は、用いるモノマー成分や組成比を適宜変えることにより前記範囲内に調整することができる。
前記ポリオールとしては、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリカプロラクトンポリオール等が挙げられる。
前記ポリイソシアネート化合物としては、例えば、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート等が挙げられる。
尚、本発明において「固形分」とは、粘着剤組成物から溶剤を除いた成分を意味する。
本発明の粘着剤組成物は、パーフルオロポリエーテル化合物(A)と粘着剤(B)を含めばよく、本発明の効果を損なわない範囲において、各種添加剤等のその他の成分を任意に含むことができる。
前記イソシアネート化合物の市販品としては、例えば、商品名タケネート300S、タケネート500、タケネート600、タケネートD165N、タケネートD178N(以上、武田薬品工業社製)、スミジュールT80、スミジュールL、デスモジュールN3400(以上、住化バイエルウレタン社製)、ミリオネートMR、ミリオネートMT、コロネートL、コロネートHL、コロネートHX(以上、日本ポリウレタン工業社製)等が挙げられる。
これらイソシアネート化合物は、単独で使用してもよく、2種以上混合して使用してもよく、2官能のイソシアネート化合物と3官能以上のイソシアネート化合物を併用して用いることも可能である。架橋剤を2種以上混合して用いることにより粘着性と耐反発性(曲面に対する接着性)を両立することが可能となり、より接着信頼性に優れた積層フィルムを得ることができる。
前記アジリジン誘導体としては、例えば、市販品としての商品名HDU、TAZM、TAZO(以上、相互薬工社製)等が挙げられる。
架橋剤は1種単独で使用してもよく、また2種以上を混合して使用してもよい。
上記架橋触媒として、例えばジラウリン酸ジブチルスズ、ジラウリン酸ジオクチルスズ等のスズ系触媒、トリス(アセチルアセトナト)鉄、トリス(ヘキサン-2,4-ジオナト)鉄、トリス(ヘプタン-2,4-ジオナト)鉄、トリス(ヘプタン-3,5-ジオナト)鉄、トリス(5-メチルヘキサン-2,4-ジオナト)鉄、トリス(オクタン-2,4-ジオナト)鉄、トリス(6-メチルヘプタン-2,4-ジオナト)鉄、トリス(2,6-ジメチルヘプタン-3,5-ジオナト)鉄、トリス(ノナン-2,4-ジオナト)鉄、トリス(ノナン-4,6-ジオナト)鉄、トリス(2,2,6,6-テトラメチルヘプタン-3,5-ジオナト)鉄、トリス(トリデカン-6,8-ジオナト)鉄、トリス(1-フェニルブタン-1,3-ジオナト)鉄、トリス(ヘキサフルオロアセチルアセトナト)鉄、トリス(アセト酢酸エチル)鉄、トリス(アセト酢酸-n-プロピル)鉄、トリス(アセト酢酸イソプロピル)鉄、トリス(アセト酢酸-n-ブチル)鉄、トリス(アセト酢酸-sec-ブチル)鉄、トリス(アセト酢酸-tert-ブチル)鉄、トリス(プロピオニル酢酸メチル)鉄、トリス(プロピオニル酢酸エチル)鉄、トリス(プロピオニル酢酸-n-プロピル)鉄、トリス(プロピオニル酢酸イソプロピル)鉄、トリス(プロピオニル酢酸-n-ブチル)鉄、トリス(プロピオニル酢酸-sec-ブチル)鉄、トリス(プロピオニル酢酸-tert-ブチル)鉄、トリス(アセト酢酸ベンジル)鉄、トリス(マロン酸ジメチル)鉄、トリス(マロン酸ジエチル)鉄、トリメトキシ鉄、トリエトキシ鉄、トリイソプロポキシ鉄、塩化第二鉄等の鉄系触媒を用いることができる。これら架橋触媒は、1種でもよく、2種以上を併用してもよい。
本発明の積層フィルムは、粘着層と基材層とを有し、前記粘着層は本発明の粘着剤組成物を用いて形成した層である。
本発明の積層フィルムは、基材層の少なくとも一方の面上に本発明の粘着剤組成物を塗布および架橋させることで製造できる。また、本発明の積層フィルムは、本発明の粘着剤組成物をあらかじめ架橋した粘着剤層を、基材層の少なくとも一方の面上に転写することによっても製造できる。
粘着剤組成物を基材上に塗布して積層フィルムを作製する際には、基材層上に均一に塗布できるよう、前記粘着剤組成物中に重合溶剤以外の一種以上の溶剤を新たに加えてもよい。
尚、「総厚み」とは、積層フィルムの基材層、粘着剤層および帯電防止層等の全ての層を含む厚みの合計を意味する。
前記樹脂材料の他の例としては、ポリスチレン、アクリロニトリル-スチレン共重合体等の、スチレン系ポリマー;ポリエチレン、ポリプロピレン、環状ないしノルボルネン構造を有するポリオレフィン、エチレン-プロピレン共重合体等の、オレフィン系ポリマー;塩化ビニル系ポリマー;ナイロン6、ナイロン6,6、芳香族ポリアミド等の、アミド系ポリマー;等を樹脂材料とするものが挙げられる。
前記樹脂材料のさらに他の例として、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー等が挙げられる。
上述したポリマーの2種以上のブレンド物からなる基材であってもよい。
また、基材がプラスチックフィルムであり、前記プラスチックフィルムに帯電防止処理を施すことにより、積層フィルム自身の帯電を低減し、かつ、被着体への帯電防止能が優れるものが得られる。なお、帯電防止機能を付与する方法としては、特に制限はなく、従来公知の方法を用いることができ、例えば、帯電防止剤と樹脂成分から成る帯電防止性樹脂や導電性ポリマー、導電性物質を含有する導電性樹脂を塗布する方法や導電性物質を蒸着あるいはメッキする方法、また、帯電防止剤等を練り込む方法等が挙げられる。帯電防止剤を使用する際には、滑剤を併用することもできる。
尚、本発明は下記実施例に限定されない。また、以下の説明や表中の「部」および「%」は、特に断りがない限り質量基準であり、固形分または有効成分を示すものである。
GPCの測定条件は以下の通りである。
測定装置:東ソー株式会社製高速GPC装置「HLC-8320GPC」
カラム:東ソー株式会社製「TSK GUARDCOLUMN SuperHZ-L」+東ソー株式会社製「TSK gel SuperHZM-N」+東ソー株式会社製「TSK gel SuperHZM-N」+東ソー株式会社製「TSK gel SuperHZM-N」+東ソー株式会社製「TSK gel SuperHZM-N」
検出器:RI(示差屈折計)
データ処理:東ソー株式会社製「EcoSEC Data Analysis バージョン1.07」
カラム温度:40℃
展開溶媒:テトラヒドロフラン
流速:0.35mL/分
測定試料:試料7.5mgを10mlのテトラヒドロフランに溶解し、得られた溶液をマイクロフィルターでろ過したものを測定試料とした。
試料注入量:20μl
標準試料:前記「HLC-8320GPC」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
東ソー株式会社製「A-300」
東ソー株式会社製「A-500」
東ソー株式会社製「A-1000」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
東ソー株式会社製「F-40」
東ソー株式会社製「F-80」
東ソー株式会社製「F-128」
東ソー株式会社製「F-288」
撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、下記式(a1-1-1)で表される両末端に水酸基を有するパーフルオロポリエーテル化合物20g、溶媒としてジイソプロピルエーテル20g、重合禁止剤としてp-メトキシフェノール0.02g及び中和剤としてトリエチルアミン3.1gを仕込み、空気気流下にて攪拌を開始し、フラスコ内を10℃に保ちながらアクリル酸クロライド2.7gを1時間かけて滴下した。
滴下終了後、10℃で1時間攪拌し、昇温して30℃で1時間攪拌した後、50℃に昇温して10時間攪拌することにより反応を行った。得られた反応液について、ガスクロマトグラフィー測定にてアクリル酸クロライドの消失が確認された。
複数のXは、それぞれ独立に、パーフルオロメチレン基又はパーフルオロエチレン基であり、1分子あたり、パーフルオロメチレン基が平均7個、パーフルオロエチレン基が平均8個存在するものであり、フッ素原子の数が平均46である。
GPCによる数平均分子量は1,500である。)
次いで、減圧下で溶媒を留去することによって、下記式(A1-1)で表されるポリ(パーフルオロアルキレンエーテル)鎖を有する重合性化合物(以下、「化合物(A1-1)」と略記する。)を得た。
複数のXは、それぞれ独立に、パーフルオロメチレン基又はパーフルオロエチレン基であり、1分子あたり、パーフルオロメチレン基が平均7個、パーフルオロエチレン基が平均8個存在するものであり、フッ素原子の数が平均46である。)
得られた混合液を上記ガラスフラスコに105℃で3時間かけて滴下した。滴下終了後、105℃で5時間撹拌した後、冷却し、パーフルオロポリエーテル化合物(A1)を30質量%含む溶液を得た。
ガラスフラスコに酢酸ブチル100gを仕込み、窒素雰囲気下で30分かけて95℃まで昇温した。2-(パーフルオロヘキシル)エチルアクリレート24.9g、前記式(A1-2)で表されるポリシロキサン結合を有するモノメタクリレート化合物5.9g、下記式(A2-1)で表されるエチレンオキシド鎖を有するモノアクリレート化合物6.2g、アクリル酸エチル50.4g、アクリル酸4-ヒドロキシブチル12.6g、溶媒として酢酸ブチル133.3g、ラジカル重合開始剤としてt-ブチルペルオキシ-2-エチルヘキサノエート3.0gを混合して混合液を調製した。
得られた混合液を上記ガラスフラスコに95℃で3時間かけて滴下した。滴下終了後、95℃で3時間撹拌した後、110℃で1.0時間撹拌した。その後、冷却し、パーフルオロアルキル基含有化合物(A’1)を30質量%含む溶液を得た。
アクリル系粘着剤(CT-3088:DIC社製)の固形分100部に対して、硬化剤(架橋剤)としてD-100K(DIC社製)を2.9部および得られたパーフルオロポリエーテル化合物(A1)を0.5部添加し、メチルエチルケトンで固形分が35%となるように希釈し、充分に混合して粘着剤組成物を得た。
得られた粘着剤組成物を、形成後の粘着層厚が20μmになるように、基材である50μm厚のポリエステルフィルムのコロナー処理面に、自動塗工装置バーコーター(PI-1210:テスター社製)を用いて直接塗工した。その後、85℃で3分間乾燥させて粘着層を形成した後、該粘着層にシリコーンコートされた38μm厚のポリエステルフィルムセパレーターを被覆して、積層フィルムを作製した。この積層フィルムをさらに40℃で3日間養生し、評価試験の試料とした。
<初期粘着力評価>
ガラス板に、得られた積層フィルムを2kgfローラー1往復で圧着して貼り付け、評価サンプルとした。貼付してから24時間経過後に、粘着・皮膜剥離解析装置 VPA-3(協和界面科学製)を用い、評価サンプルの粘着力を測定した。測定条件は、下記の通りである。引張速度と剥離速度を150mm/minとした場合と、引張速度と剥離速度を1,200mm/minとした場合の2パターンで粘着力を評価した。
・引張速度:150mm/min、1,200mm/min
・剥離速度:150mm/min、1,200mm/min
・剥離方向:180°
・試料サイズ:25mm×70mm
初期粘着力評価に用いるサンプルを別途作製し、当該評価サンプルを温度80℃に置いて7日間保存した。保存後(耐熱試験後)の評価サンプルを初期粘着力評価と同じ方法で粘着力を評価した。
パーフルオロポリエーテル化合物(A1)の代わりにパーフルオロアルキル基含有化合物(A’1)を用いた他は、実施例1と同様にして積層フィルムを製造し、評価した。結果を表1に示す。
パーフルオロポリエーテル化合物(A1)を加えなかった他は、実施例1と同様にして積層フィルムを製造し、評価した。結果を表1に示す。
尚、パーフルオロアルキル基含有化合物(A’1)はパーフルオロヘキシル基を有する化合物であるので、環境蓄積性が懸念される化合物である。
Claims (11)
- ポリ(パーフルオロアルキレンエーテル)鎖(a1)を有するパーフルオロポリエーテル化合物(A)と、粘着剤(B)とを含有する粘着剤組成物。
- 前記化合物(A)が、ポリオキシアルキレン鎖(a2)及び/又はシリコーン鎖(a3)を有する請求項1に記載の粘着剤組成物。
- 前記化合物(A)が、ポリ(パーフルオロアルキレンエーテル)鎖(a1)を主鎖に有し、ポリオキシアルキレン鎖(a2)及び/又はシリコーン鎖(a3)を側鎖に有する重合体である請求項1又は2に記載の粘着剤組成物。
- 前記化合物(A)が、ポリ(パーフルオロアルキレンエーテル)鎖(a1)を有する重合性単量体と、ポリオキシアルキレン鎖(a2)を含む重合性単量体及びシリコーン鎖(a3)を含む重合性単量体からなる群から選択される1種以上とを重合成分とする共重合体である請求項1~3のいずれかに記載の粘着剤組成物。
- 前記ポリ(パーフルオロアルキレンエーテル)鎖(a1)を有する重合性単量体が、ポリ(パーフルオロアルキレンエーテル)鎖(a1)の両末端に重合性不飽和基を有する化合物である請求項4に記載の粘着剤組成物。
- 前記化合物(A)が、炭素原子数が6以上のパーフルオロアルキル基を有さない請求項1~5のいずれかに記載の粘着剤組成物。
- 前記化合物(A)がフッ素化アルキル基を有さない請求項1~6のいずれかに記載の粘着剤組成物。
- 前記化合物(A)の含有率が、粘着剤組成物の固形分中0.01~20質量%の範囲である請求項1~7のいずれかに記載の粘着剤組成物。
- 前記粘着剤(B)がアクリル系粘着剤(b1)及び/又はウレタン系粘着剤(b2)である請求項1~8のいずれかに記載の粘着剤組成物。
- 請求項1~9のいずれかに記載の粘着剤組成物の粘着層と基材層とを有する積層フィルム。
- 光学部材の表面保護フィルムである請求項10記載の積層フィルム。
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