WO2020217820A1 - 粘着剤用組成物、粘着フィルム、及び表面保護フィルム - Google Patents
粘着剤用組成物、粘着フィルム、及び表面保護フィルム Download PDFInfo
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- WO2020217820A1 WO2020217820A1 PCT/JP2020/013054 JP2020013054W WO2020217820A1 WO 2020217820 A1 WO2020217820 A1 WO 2020217820A1 JP 2020013054 W JP2020013054 W JP 2020013054W WO 2020217820 A1 WO2020217820 A1 WO 2020217820A1
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1565—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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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
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- 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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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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
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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]
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Definitions
- Embodiments of the present invention relate to adhesive compositions, adhesive films, and surface protective films.
- An optical film such as a polarizing plate is used for the display.
- a surface protective film may be attached to the surface of the optical film.
- the surface protective film protects the surface of the optical film, and can prevent scratches and stains from being attached in the process of transporting and manufacturing the display.
- the surface protective film includes a base film and an adhesive film formed on one side of the base film so that the surface protective film does not shift from the optical film. Since the appearance inspection of the optical film may be performed with the surface protective film bonded to the optical film, a highly transparent acrylic adhesive is widely used for the adhesive film. Further, the surface protective film is peeled off from the optical film and removed when it is no longer needed. Usually, a slightly adhesive adhesive is used for the adhesive film so that the surface protective film can be easily peeled off when the surface protective film is peeled off.
- the surface protective film is required to have a property that the adhesive does not easily remain on the optical film after peeling.
- Cited Document 1 discloses a pressure-sensitive adhesive composition containing an ionic liquid and an acrylic polymer as a pressure-sensitive adhesive composition used for forming a surface protective film. Further, in Cited Document 2, a pressure-sensitive adhesive layer formed on the surface of the base film is provided, and the acrylic pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains at least an antistatic agent and a compound containing fluorine or silicon. A surface protective film characterized by being attached is disclosed.
- the present invention includes various embodiments. Examples of embodiments are listed below. The present invention is not limited to the following embodiments.
- One embodiment relates to a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A), an alkali metal salt (B), and a compound (C) represented by the formula (I).
- X independently represents an oxygen atom or a nitrogen atom
- R independently represents a hydrogen atom, an alkyl group, or a fluoroalkyl group.
- the pressure-sensitive adhesive composition may further contain a cross-linking agent (D).
- D cross-linking agent
- the (meth) acrylic polymer (A) comprises a structural unit derived from an alkyl (meth) acrylate monomer and a structural unit derived from a (meth) acrylic monomer having a hydroxyl group or a carboxyl group. Is preferable.
- Another embodiment relates to an adhesive film obtained by using the composition for an adhesive.
- Another embodiment relates to a surface protective film having an adhesive film obtained by using the composition for an adhesive and a base film.
- a composition for an adhesive that can produce an adhesive film having excellent antistatic properties and low contamination properties. Further, according to another embodiment of the present invention, it is possible to provide an adhesive film having excellent antistatic property and low pollution property. Furthermore, according to another embodiment of the present invention, it is possible to provide a surface protective film having an adhesive film having excellent antistatic properties and low stain resistance.
- FIG. 1 is a schematic cross-sectional view showing an example of a surface protective film according to an embodiment.
- the pressure-sensitive adhesive composition according to the embodiment of the present invention contains a (meth) acrylic polymer (A), an alkali metal salt (B), and a compound (C) represented by the formula (1).
- the pressure-sensitive adhesive composition may further contain any component such as a cross-linking agent (D) and various additives.
- the composition for a pressure-sensitive adhesive containing the (meth) acrylic polymer (A), the alkali metal salt (B), and the compound (C) represented by the formula (1) is excellently charged. It is possible to achieve both preventability and low pollution.
- the (meth) acrylic polymer (A) is a polymer containing a structural unit derived from the (meth) acrylic monomer.
- the (meth) acrylic monomer has at least one (meth) acryloyl group in the molecule.
- (meth) acrylic monomer is a general term for an acrylic monomer and a methacrylic monomer
- (meth) acryloyl group is a general term for an acryloyl group and a methacryloyl group.
- the structural unit derived from the (meth) acrylic monomer preferably contains at least one structural unit derived from the alkyl (meth) acrylate monomer (M1).
- the structural unit derived from the (meth) acrylic monomer may contain two or more structural units derived from the alkyl (meth) acrylate monomer (M1).
- the alkyl (meth) acrylate monomer (M1) preferably contains a monomer represented by the following formula (m1) (hereinafter, may be referred to as "monomer (m1)").
- R 1a represents a hydrogen atom or a methyl group
- R 1b represents an alkyl group
- the alkyl group may be linear, branched, or cyclic.
- the alkyl group is preferably a linear alkyl group.
- the number of carbon atoms of the alkyl group is preferably 1 to 22, more preferably 1 to 16, and even more preferably 1 to 12.
- the alkyl (meth) acrylate monomer (M1) includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl.
- the content of the alkyl (meth) acrylate monomer (M1) is preferably 99 parts by mass or less, preferably 95 parts by mass or less, based on a total of 100 parts by mass of all the monomers. Is more preferable, and 90 parts by mass or less is further preferable.
- the structural unit derived from the (meth) acrylic monomer preferably contains at least one structural unit derived from the (meth) acrylic monomer (M2) having a hydroxyl group or a carboxyl group.
- the (meth) acrylic monomer (M2) has at least a hydroxyl group, a carboxyl group, or both a hydroxyl group and a carboxyl group.
- the structural unit derived from the (meth) acrylic monomer may contain two or more structural units derived from the (meth) acrylate monomer (M2).
- the (meth) acrylic monomer (M2) is preferably a monomer represented by the following formula (m2-1) (hereinafter, may be referred to as “monomer (m2-1)”), the following formula (m2-2). It contains at least one selected from the group consisting of a monomer represented by (hereinafter, may be referred to as “monomer (m2-2)”) and (meth) acrylic acid.
- the (meth) acrylic monomer (M2) more preferably contains a monomer (m2-1).
- R 2a represents a hydrogen atom or a methyl group
- R 2b represents a divalent linking group
- R 3a represents a hydrogen atom or a methyl group
- R 3b represents a divalent linking group
- the divalent linking group contains, for example, one or more groups selected from the group consisting of an alkylene group, an oxy group, and a carbonyl group. Is preferable.
- the alkylene group may be linear, branched or cyclic.
- the alkylene group is preferably a linear alkylene group.
- the alkylene group preferably has 1 to 22 carbon atoms, more preferably 1 to 16 carbon atoms, and even more preferably 1 to 12 carbon atoms.
- the divalent linking group is more preferably an alkylene group and even more preferably a linear alkylene group.
- the (meth) acrylic monomer (M2) is, for example, hydroxy such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate.
- the (meth) acrylic monomer (M2) more preferably contains, for example, at least one selected from the group consisting of hydroxyalkyl (meth) acrylate and (meth) acrylic acid, and preferably contains hydroxyalkyl (meth) acrylate. Is more preferable.
- the content thereof is 0.1 parts by mass based on 100 parts by mass in total of all the monomers. It is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and particularly preferably 2.5 parts by mass or more. When the content is 0.1 part by mass or more, sufficient adhesiveness tends to be easily obtained.
- the content of the (meth) acrylic monomer (M2) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 14 parts by mass or less based on a total of 100 parts by mass of all the monomers. It is more preferable that the amount is 12 parts by mass or less. When the content is 20 parts by mass or less, the effect of preventing contamination of the adherend tends to be easily obtained.
- the structural unit derived from the (meth) acrylic monomer is different from the structural unit derived from the alkyl (meth) acrylate monomer (M1) and the structural unit derived from the (meth) acrylate monomer (M2), and other (meth) acrylics. It may contain at least one structural unit derived from the monomer (M3).
- the structural unit derived from the (meth) acrylic monomer may contain two or more types of structural units derived from the (meth) acrylic monomer (M3).
- the (meth) acrylic monomer (M3) preferably contains a (poly) oxyalkylene group-containing (meth) acrylic monomer such as (poly) alkylene glycol monoalkyl ether mono (meth) acrylate.
- a (poly) alkylene glycol is a general term for "alkylene glycol” and “polyalkylene glycol”
- “(poly) oxyalkylene” is a general term for "oxyalkylene” and "polyoxyalkylene”. ..
- the content thereof is 1 part by mass or more based on 100 parts by mass in total of all the monomers. It is preferably 2 parts by mass or more, and further preferably 3 parts by mass or more.
- the content of the (meth) acrylic monomer (M3) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass or less based on a total of 100 parts by mass of all the monomers. Is more preferable.
- the (meth) acrylic polymer (A) may contain other structural units different from the structural units derived from the (meth) acrylic monomer.
- other structural units for example, vinyl ester-based monomers such as vinyl acetate; styrene-based monomers such as styrene and sodium styrene sulfonate; olefin-based monomers such as butadiene; vinyl such as halogen-containing monomers such as vinyl chloride and tetrafluoroethylene.
- Examples include structural units derived from group-containing monomers.
- the (meth) acrylic polymer (A) preferably contains a structural unit derived from the (meth) acrylic monomer (M2), and contains a structural unit derived from the alkyl (meth) acrylate monomer (M1) and the (meth) acrylic monomer. It is more preferable to include a structural unit derived from (M2).
- the polymerization method of the (meth) acrylic polymer (A) is not particularly limited.
- a polymerization method of the (meth) acrylic polymer (A) known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization can be used.
- a compound that generates radicals by heat can be used.
- organic peroxides such as benzoyl peroxide and lauroyl peroxide
- azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2-methylbutyronitrile). And so on.
- the glass transition temperature (Tg) of the (meth) acrylic polymer (A) is preferably 0 ° C. or lower, more preferably ⁇ 5 ° C. or lower, and even more preferably ⁇ 10 ° C. or lower.
- the glass transition temperature of the (meth) acrylic polymer (A) is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 40 ° C. or higher, and even more preferably ⁇ 25 ° C. or higher.
- the ratios, Tg1, Tg2, ..., Tgn are the glass transition temperatures of the homopolymers of each monomer.
- Various literature values can be used as the glass transition temperatures of the homopolymers used in this calculation.
- the glass transition temperature of homopolymers is described in, for example, the acrylic ester catalog of Mitsubishi Rayon Co., Ltd. (1997 edition), New Polymer Bunko 7, "Introduction to Synthetic Resins for Paints", Polymer Publishing Association, and Kyozo Kitaoka. ing.
- Examples of the method for adjusting the glass transition temperature of the (meth) acrylic polymer (A) include the following methods.
- the glass transition temperature can be lowered by using an alkyl (meth) acrylate having a large number of carbon atoms.
- the glass transition temperature can be increased by using an alkyl (meth) acrylate having a small number of carbon atoms.
- the use of methacrylate also tends to increase the glass transition temperature.
- the weight average molecular weight of the (meth) acrylic polymer (A) is preferably 50,000 or more, more preferably 80,000 or more, and even more preferably 100,000 or more.
- the weight average molecular weight of the (meth) acrylic polymer (A) is preferably 800,000 or less, more preferably 700,000 or less, and even more preferably 600,000 or less.
- the weight average molecular weight is a value obtained by conversion by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. Specifically, the measurement method described in the examples may be followed.
- GPC gel permeation chromatography
- the weight average molecular weight is 50,000 or more, an adhesive film having good adhesive strength tends to be obtained.
- the weight average molecular weight is 800,000 or less, it is easy to prevent the pressure-sensitive adhesive composition from becoming highly viscous.
- the pressure-sensitive adhesive composition may contain only one type of (meth) acrylic polymer (A) or may contain two or more types of (meth) acrylic polymer (A).
- the alkali metal salt (B) contains an alkali metal ion and a counter anion. It is considered that the pressure-sensitive adhesive composition contains the alkali metal salt (B) to impart conductivity to the pressure-sensitive adhesive film, so that the pressure-sensitive adhesive film exhibits good antistatic properties.
- the alkali metal salt (B) preferably contains at least one selected from the group consisting of lithium ion, sodium ion, and potassium ion as the alkali metal ion, and is selected from the group consisting of lithium ion and sodium ion. It is more preferable to contain at least one kind, and it is further preferable to contain lithium ions. When lithium ions are contained, better antistatic properties can be obtained.
- the counter anion is, for example, chlorine ion, perchlorate ion, hexafluorophosphate ion, hexafluoroarsenate ion, tetrafluoroborate ion, tetraphenylborate ion, trifluoromethanesulfonate ion, bis (trifluoromethanesulfonyl). It preferably contains at least one selected from the group consisting of imide ions and bis (pentafluoroethanesulfonyl) imide ions.
- the alkali metal salt (B) a salt represented by the following formula can be mentioned (hereinafter, the salt represented by the formula (b1) may be referred to as “salt (b1)”.
- Formula (b2) The same applies to the salt represented by any of (b6).
- M represents an alkali metal ion
- R represents a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, or a fluoroaryl group
- R 1 and R 2 are independent fluorine atoms, respectively.
- the number of carbon atoms of the alkyl group and the fluoroalkyl group is preferably 1 to 6, and more preferably 1 to 4.
- a fluoroalkyl group is a fluoroalkyl group in which some of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms, but a fluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms (that is, perfluoroalkyl). Group), preferably a perfluoroalkyl group.
- the aryl group and the fluoroaryl group preferably have 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms.
- a fluoroaryl group is a fluoroaryl group in which some of the hydrogen atoms contained in the aryl group are substituted with fluorine atoms, but all of the hydrogen atoms are substituted with fluorine atoms (that is, perfluoroaryl). Group), preferably a perfluoroaryl group.
- the alkali metal salt (B) preferably contains at least one selected from the group consisting of salt (b1) to salt (b6), and is composed of salt (b1), salt (b5), and salt (b6). It is more preferable to include at least one selected from the group, and even more preferably to include at least one selected from the group consisting of salt (b1) and salt (b5).
- the alkali metal salt (B) contains the salt (b5) from the viewpoints of good compatibility with the (meth) acrylic polymer (A), chlorine-free, and easy liberation of alkali metal ions. Is preferable.
- alkali metal salt (B) examples include lithium chloride (LiCl), lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium hexafluorophosphate (LiAsF 6 ), and tetrafluoro.
- Lithium borate LiBF 4 ), lithium tetraphenylborate (LiB (C 6 H 5 ) 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), bis (trifluoromethanesulfonyl) imide lithium (LiN (CF 3 SO)) 2 ) 2 ), Lithium salts such as bis (pentafluoroethanesulfonyl) imidelithium (LiN (C 2 F 5 SO 2 ) 2 ); sodium chloride (NaCl), sodium perchlorate (NaClO 4 ), hexafluorophosphate sodium (NaPF 6), sodium hexafluoroarsenate (NaAsF 6), sodium tetrafluoroborate (NaBF 4), sodium tetraphenyl borate (NaB (C 6 H 5) 4), sodium trifluoromethanesulfonate (NaCF 3 Sodium salts such as SO
- the alkali metal salt (B) preferably has a melting point of more than 25 ° C. and is a solid salt at room temperature (for example, 25 ° C.).
- a salt that is solid at room temperature is preferable from the viewpoint of preventing contamination of the adherend by the adhesive film because it does not easily flow out from the adhesive film.
- the pressure-sensitive adhesive composition may contain only one type of alkali metal salt (B) or may contain two or more types of alkali metal salt (B).
- the content of the alkali metal salt (B) is preferably 0.1 part by mass or more, and more preferably 0.2 part by mass or more, based on 100 parts by mass of the (meth) acrylic polymer (A). It is preferably 0.5 parts by mass or more, and more preferably 0.5 parts by mass or more. When it is 0.1 part by mass or more, better antistatic property can be obtained.
- the content of the alkali metal salt (B) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, based on 100 parts by mass of the (meth) acrylic polymer (A), and 5 parts by mass. It is more preferably less than a part. When it is 10 parts by mass or less, better low pollution property can be obtained.
- the pressure-sensitive adhesive composition contains the compound (C) represented by the following formula (I).
- the compound (C) promotes the movement of the alkali metal ions contained in the alkali metal salt (B), and the antistatic property is enhanced.
- X independently represents an oxygen atom or a nitrogen atom
- R independently represents a hydrogen atom, an alkyl group, or a fluoroalkyl group.
- X is an oxygen atom
- -X- contained in the formula (I) represents -O-
- X is a nitrogen atom
- a hydrogen atom may be bonded to the nitrogen atom
- -X- contained in the formula (I) can be represented by -NH-.
- the alkyl group may be linear, branched or cyclic.
- the alkyl group is preferably a group represented by ⁇ C n H 2n + 1 (n is an integer of 1 or more). n is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4.
- the fluoroalkyl group may be linear, branched or cyclic.
- the fluoroalkyl group is represented by ⁇ C n Hm F 2n + 1-m (n is an integer of 1 or more, m is an integer of 0 or more, where m is an integer of 2n or less). It is preferably a group.
- n is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4.
- m is preferably 0 to 2n, more preferably 0 to n, and even more preferably 0.
- the compound in which R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a fluoroalkyl group having 1 to 12 carbon atoms, respectively, improves the low contamination property of the adhesive film. It is a preferable compound from the viewpoint of causing.
- Examples of the compound (C) include a cyclic carbonate compound and a cyclic urea compound.
- Specific examples of the compound (C) include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, trans-2,3-butylene carbonate, cis-2,3-butylene carbonate, 1,2-pentylene carbonate, and the like.
- Cyclic carbonate compounds such as trans-2,3-pentylene carbonate, cis-2,3-pentylene carbonate, fluoroethylene carbonate, trifluoromethylethylene carbonate, 4,5-difluoroethylene carbonate; and 2-imidazolidinone. It is preferable to contain at least one selected from the group consisting of cyclic urea compounds such as.
- the cyclic carbonate compound is represented by the formula (I) and is a compound in which two Xs are oxygen atoms.
- the cyclic urea compound is represented by the formula (I) and is a compound in which two Xs are nitrogen atoms.
- the compound (C) preferably contains a cyclic carbonate compound, and more preferably contains at least one selected from the group consisting of ethylene carbonate and propylene carbonate. From the viewpoint of conductivity, the compound (C) preferably contains at least ethylene carbonate.
- the compound (C) is preferably a compound having a melting point of more than 25 ° C.
- a compound having a melting point of more than 25 ° C. is preferable from the viewpoint of preventing contamination of the adherend by the adhesive film because it does not easily flow out from the adhesive film.
- the pressure-sensitive adhesive composition may contain only one compound (C) or two or more compounds (C).
- the content of the compound (C) is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the (meth) acrylic polymer (A). It is more preferably 1 part by mass or more. When it is 0.2 parts by mass or more, better antistatic property can be obtained.
- the content of the compound (C) is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and 8 parts by mass or less, based on 100 parts by mass of the (meth) acrylic polymer (A). Is more preferable. When it is 15 parts by mass or less, better low pollution property can be obtained.
- the pressure-sensitive adhesive composition may contain a cross-linking agent (D).
- the cross-linking agent (D) preferably contains, for example, at least one selected from the group consisting of an isocyanate compound, an epoxy compound, a (meth) acrylate compound, and a metal chelate compound. Since the cross-linking reaction can be promoted by heating, the cross-linking agent (D) more preferably contains at least one selected from the group consisting of, for example, an isocyanate compound and an epoxy compound, and further preferably contains an isocyanate compound. ..
- the isocyanate compound may be a bifunctional or higher functional isocyanate compound.
- the isocyanate compound preferably contains at least one selected from the group consisting of a bifunctional isocyanate compound and a trifunctional or higher functional isocyanate compound.
- the isocyanate compound may contain only a bifunctional isocyanate compound, or may contain only a trifunctional or higher functional isocyanate compound.
- the isocyanate compound may include a bifunctional isocyanate compound and a trifunctional or higher functional isocyanate compound.
- the bifunctional isocyanate compound may be one or more selected from compounds having two isocyanate (-NCO) groups in one molecule.
- the bifunctional isocyanate compound for example, an aliphatic diisocyanate; an aromatic diisocyanate; at least one adduct selected from an aliphatic diisocyanate and an aromatic diisocyanate; selected from an aliphatic diisocyanate and an aromatic diisocyanate.
- At least one alofanate compound and the like can be mentioned.
- the "at least one adduct selected from aliphatic diisocyanates and aromatic diisocyanates” is, for example, an adduct of at least one selected from aliphatic diisocyanates and aromatic diisocyanates and a bifunctional polyol.
- a bifunctional polyol is a compound having two hydroxyl (-OH) groups in one molecule. Examples of the bifunctional polyol include ethylene glycol and propylene glycol.
- aliphatic diisocyanate examples include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), hydrogenated xylylene diisocyanate (H6XDI) and the like.
- aromatic diisocyanate examples include diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), dimethyldiphenylenediocyanate (TOID), and tolylene diisocyanate (TDI).
- the trifunctional or higher functional isocyanate compound may be one or more selected from compounds having three or more isocyanate groups in one molecule, and may be selected from compounds having three isocyanate groups in one molecule. It is preferable that one kind or two or more kinds are used.
- Examples of the trifunctional or higher functional isocyanate compound include an adduct compound of a bifunctional isocyanate compound; an isocyanurate compound of a bifunctional isocyanate compound; and a biuret compound of a bifunctional isocyanate compound.
- the "adduct of a bifunctional isocyanate compound” is, for example, an adduct of a bifunctional isocyanate compound and a trifunctional or higher functional polyol.
- a trifunctional or higher functional polyol is a compound having three or more hydroxyl ( ⁇ OH) groups in one molecule. Examples of trifunctional or higher functional polyols include trimethylolpropane (TMP) and glycerin.
- isocyanate compound examples include an isocyanate compound represented by the following formula (hereinafter, the isocyanate compound represented by the formula (d1) may be referred to as “isocyanate compound (d1)”.
- isocyanate compound (d2) Formulas (d2) to The same applies to the isocyanate compound represented by any of (d6)).
- R independently represents a divalent organic group
- R 1 represents a monovalent substituent
- R 2 represents a divalent organic group
- R 3 represents a trivalent organic group. Represents an organic group.
- R is preferably a substituted or unsubstituted hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group; an alicyclic hydrocarbon group; or an aromatic hydrocarbon group. .. Aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups may be substituted or unsubstituted.
- the aliphatic hydrocarbon group is preferably an alkylene group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 22, more preferably 1 to 12, and even more preferably 1 to 8.
- the alicyclic hydrocarbon group is preferably a cycloalkylene group.
- the number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 5 to 8, and even more preferably 6.
- the number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6.
- the aromatic hydrocarbon group may have at least one substituent selected from the group consisting of linear or branched aliphatic hydrocarbon groups and alicyclic hydrocarbon groups.
- R as the hydrocarbon group, methylene group, ethylene group, propylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, pentamethylene group, 1 -Methyltetramethylene group, 2-methyltetramethylene group, hexamethylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group Linear or branched aliphatic hydrocarbon groups such as groups, heptamethylene groups and octamethylene groups; alicyclic hydrocarbon groups such as cyclopentylene group, cyclohexylene group and cycloheptylene group; phenylene group, tolylen group, Examples include aromatic hydrocarbon groups such as a xylylene group and a naphthylene group.
- R 1 may be a substituent containing a hydroxyl group.
- R 2 is preferably a substituted or unsubstituted hydrocarbon group, and preferably a substituted or unsubstituted alkylene group.
- R 3 is preferably a substituted or unsubstituted hydrocarbon group, and preferably a substituted or unsubstituted alkane-triyl group. When the hydrocarbon group has a substituent, the substituent includes a hydroxyl group.
- the isocyanate compound preferably contains at least one selected from the group consisting of isocyanate compounds (d1) to (d6), and contains at least one selected from the group consisting of isocyanate compounds (d2) to (d6). Is more preferable.
- the isocyanate compound preferably contains at least one selected from the group consisting of the isocyanate compounds (d3) and (d4), and the isocyanate compound (d3). It is more preferable to include.
- the content of the cross-linking agent (D) is 0.1 part by mass or more based on 100 parts by mass of the (meth) acrylic polymer (A). It is preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more.
- the content of the cross-linking agent (D) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the (meth) acrylic polymer (A), and 10 parts by mass. The following is more preferable.
- the pressure-sensitive adhesive composition may contain the cross-linking agent (D) alone or in combination of two or more.
- the pressure-sensitive adhesive composition may contain a curing accelerator.
- the curing accelerator preferably accelerates the reaction rate of the functional group contained in the (meth) acrylic polymer and the functional group contained in the curing agent (D).
- the functional group refers to a (meth) acryloyl group, a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group and the like.
- an organometallic compound for example, an organometallic compound, a tertiary amine compound, or the like can be used.
- the organometallic compound include tin-based catalysts such as dibutyltin dilaurate, dibutyltin dichloride, and dibutyltin oxide.
- the pressure-sensitive adhesive composition may contain a solvent.
- the solvent is preferably an organic solvent.
- the organic solvent include formic acid, acetic acid, methanol, ethanol, propanol, methyl cellosolve, cellosolve, acetone, acetylacetone, acetonitrile, hexane, benzene, toluene, dichloromethane, ethyl acetate, butyl acetate, chlorobenzene, dichlorobenzene and the like.
- the pressure-sensitive adhesive composition may contain other optional components.
- Other optional components include surfactants, plasticizers, fillers, curing retardants, processing aids, anti-aging agents, antioxidants and the like.
- the pressure-sensitive adhesive composition may contain other optional components alone or in combination of two or more.
- the pressure-sensitive adhesive film according to the embodiment of the present invention is a film obtained by using the above-mentioned pressure-sensitive adhesive composition.
- the (meth) acrylic polymer (A) may be crosslinked.
- the method for producing the adhesive film is not particularly limited, and a known production method may be used.
- the pressure-sensitive adhesive film can be obtained, for example, by forming a layer of the pressure-sensitive adhesive composition on the surface of the support film and drying and / or curing the layer of the pressure-sensitive adhesive composition.
- the adhesive film can be formed, for example, by an extrusion method.
- the adhesive film formed on the support film may be used after being peeled from the support film, or may be used in the state of a laminate having the adhesive film and the support film without peeling from the support film. ..
- a known coating method, a known printing method, or the like can be applied to the method of forming the layer of the pressure-sensitive adhesive composition.
- coating methods such as cast coating, spray coating, spin coating, dip coating, bar coating, comma coating, blade coating, die coating; intaglio printing such as gravure printing, stencil printing such as screen printing, etc. Can be mentioned.
- the layer of the pressure-sensitive adhesive composition can be dried and cured by heating.
- the heating temperature can be, for example, 50 to 150 ° C.
- the heating time can be, for example, 1 minute to 10 hours.
- the thickness of the adhesive film is not particularly limited.
- the thickness of the adhesive film is, for example, preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 5 ⁇ m or more. When the thickness of the adhesive film is 1 ⁇ m or more, sufficient strength can be maintained, and good adhesiveness tends to be easily obtained.
- the thickness of the adhesive film is, for example, preferably 20 ⁇ m or less, more preferably 18 ⁇ m or less, and further preferably 15 ⁇ m or less. When it is 20 ⁇ m or less, sufficient flexibility can be maintained, the adhesive film tends to easily follow the shape of the adherend, and the adhesive film tends to be easily prevented from peeling off from the adherend.
- the surface resistivity of the adhesive film is preferably 1.0 ⁇ 10 12 ⁇ / ⁇ or less, more preferably 5.0 ⁇ 10 11 ⁇ / ⁇ or less, and 2.5 ⁇ 10 11 ⁇ / ⁇ or less.
- the following is more preferable.
- it is 1.0 ⁇ 10 12 ⁇ / ⁇ or less, it is possible to effectively suppress the generation of static electricity due to charging when the adhesive film is peeled off from the adherend. As a result, the peeling band voltage caused by static electricity generated when the adhesive film is peeled from the adherend can be reduced, and the influence on the adherend can be suppressed. If the peeling band voltage is high, problems may occur due to a phenomenon in which dust adheres to the adherend, a phenomenon in which circuit components arranged in the vicinity of the adherend are destroyed, and the like.
- the adhesive film preferably has no adhesive attached to the adherend. Adhesion of the adhesive may cause a poor appearance of the adherend.
- the adhesive film is attached to the adherend and allowed to stand in a high temperature and high humidity condition of 85 ° C. and 85% RH (RH: relative humidity) for a predetermined time. After that, the adhesive film is peeled off from the adherend, and the presence or absence of the adhesive adhered to the adherend is visually confirmed.
- the "predetermined time" can be 3, 20, or 40 days.
- the surface protective film according to the embodiment of the present invention has an adhesive film obtained by using the composition for an adhesive and a base film.
- the surface protective film may have any other film such as a cover film.
- examples thereof include a surface protective film having an adhesive film and a cover film provided on a surface opposite to the base film of the adhesive film.
- FIG. 1 is a schematic cross-sectional view showing an example of a surface protective film.
- the surface protective film 1 is formed on the base film 4, the adhesive film 3 provided on one surface of the base film 4, and the adhesive film 3 on the surface opposite to the base film 4. It has a cover film 2 provided.
- the base film preferably has a plastic film.
- the base film may have an arbitrary layer such as an antistatic layer, an antifouling layer, and an adhesion-imparting layer provided on at least one surface of the plastic film.
- an antistatic layer and / or an antifouling layer it is preferable that the antistatic layer and / or the antifouling layer is provided on the surface of the base film opposite to the adhesive film.
- the base film may have only one type of arbitrary layer, or may have two or more types in combination.
- At least one surface of the plastic film may be subjected to surface treatment such as antistatic treatment, antifouling treatment, adhesion imparting treatment, corona treatment, and plasma treatment.
- surface treatment such as antistatic treatment, antifouling treatment, adhesion imparting treatment, corona treatment, and plasma treatment.
- antistatic treatment include application and kneading of an antistatic agent.
- the antistatic treatment and / or antifouling treatment may be applied to the surface of the base film opposite to the adhesive film.
- Only one type of surface treatment may be applied to the base film, or two or more types may be applied in combination.
- a known antistatic agent can be used for the antistatic layer and the antistatic treatment.
- known mold release agents such as silicone-based mold release agents and fluorine-based mold release agents
- known antifouling agents such as silica fine particles
- the plastic film is preferably a polyester film.
- Plastic films include, for example, polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene ( Selected from the group consisting of PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer (COC), cycloolefin polymer (COP), norbornene resin containing norbornene, polyether sulfone, cellophane, and aromatic polyamide. It is preferable that the film contains at least one of them.
- the thickness of the base film is not particularly limited.
- the thickness of the base film is, for example, preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more, and further preferably 50 ⁇ m or more. When the thickness of the base film is 10 ⁇ m or more, sufficient strength can be maintained, and good film winding property and processability tend to be easily obtained.
- the thickness of the base film is, for example, preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and further preferably 100 ⁇ m or less. When it is 200 ⁇ m or less, sufficient flexibility can be maintained, the surface protective film tends to easily follow the shape of the adherend, and the surface protective film tends to be easily prevented from peeling from the adherend.
- the cover film preferably has a plastic film.
- the cover film preferably has a plastic film and a release layer provided on the surface of the plastic film on the adhesive film side.
- it is preferable that the surface of the plastic film on the adhesive film side is subjected to a mold release treatment.
- a known release agent such as a silicone-based release agent or a fluorine-based release agent can be used for the release layer and the release treatment.
- the plastic film is preferably a film containing at least one selected from the group consisting of the polymer and the resin mentioned as an example of the plastic film in the description of the base film, and more preferably a polyester film. ..
- the thickness of the cover film is not particularly limited.
- the thickness of the cover film is, for example, preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more, and further preferably 50 ⁇ m or more.
- the thickness of the cover film is, for example, preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and further preferably 100 ⁇ m or less.
- the method for producing the surface protective film is not particularly limited, and a known method may be used.
- the surface protective film can be obtained, for example, by forming an adhesive film on one surface of the base film.
- the surface protective film can be obtained by forming a layer of the pressure-sensitive adhesive composition on one surface of the base film and drying and / or curing the layer of the pressure-sensitive adhesive composition. ..
- the surface protective film can be formed by, for example, a co-extrusion method.
- the method for producing the adhesive film mentioned in the description of the adhesive film can be used.
- a base film may be used instead of the support film.
- the protection target by the surface protection film is not particularly limited.
- the surface protective film can be used by being attached so that the surface on the adhesive film side is in contact with the protection target.
- the surface protective film may be attached to the protection target after the cover film is peeled off.
- protection targets include optical members such as polarizing plates, liquid crystal displays (LCDs), plasma displays (PDPs), cathode ray tubes (CRTs), electric field emission displays (FEDs), organic EL displays, 3D displays, electronic papers, and the like. Examples include display devices, automobile parts, home appliance parts, mobile terminals, electronic parts, and building materials.
- Example A1 In a reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen introduction tube, 90 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of 4-hydroxybutyl acrylate, 50 parts by mass of ethyl acetate as a solvent, and azo as a polymerization initiator. 0.1 parts by mass of bisisobutyronitrile was added. Then, nitrogen gas was introduced and the air in the reaction system was replaced with nitrogen gas over 1 hour. Then, the reaction was carried out at 75 ° C. for 7 hours to obtain a solution of a (meth) acrylic polymer (A-1) having a weight average molecular weight of 500,000.
- the weight average molecular weight of the (meth) acrylic polymer is a value obtained by measuring by a gel permeation chromatography (GPC) method and converting by a standard polystyrene calibration curve.
- GPC gel permeation chromatography
- the glass transition temperature (Tg) of the (meth) acrylic polymer was determined by the above-mentioned FOX formula.
- As the glass transition temperature of the homopolymer the value described in "Introduction to Synthetic Resins for Paints” was used.
- Examples A2 to 10 and Comparative Examples A1 to 7 Solutions of (meth) acrylic polymers (A-2) to (A-4) were obtained in the same manner as in Example A1 except that the monomers shown in Table 1 were used. Then, the adhesive compositions of Examples A2 to A10 and Comparative Examples A1 to A7 were obtained in the same manner as in Example A1 except that the components shown in Tables 2 and 3 were used.
- the (meth) acrylic polymer (A-5) is "SK Dyne (registered trademark) 1499M” manufactured by Soken Chemical Co., Ltd. Tables 1 to 3 show the amount of solid content (parts by mass) of each component.
- Table 4 shows the explanation of the abbreviations used in Tables 1 to 3.
- (B-1) and (B-2) are alkali metal salts having a melting point of more than 25 ° C. and a solid at a temperature of 25 ° C.
- (B-1) is an alkaline earth metal salt having a melting point of more than 25 ° C. and a solid at a temperature of 25 ° C.
- (C-1) is a compound (C) represented by the formula (I), which has a melting point of 36 ° C. and is a solid compound at a temperature of 25 ° C.
- (C-2) is a compound (C) represented by the formula (I), which has a melting point of ⁇ 55 ° C. and is a liquid compound at a temperature of 25 ° C.
- (C-1) to (c-3) are polyalkylene glycols, and both (c-1) and (c-2) are liquid compounds at a temperature of 25 ° C.
- (C-3) is a polyalkylene glycol, which is a solid compound at a temperature of 25 ° C.
- Example B1 The pressure-sensitive adhesive composition of Example A1 was applied onto a polyethylene terephthalate (PET) film, heated at 110 ° C. for 2 minutes, dried and cured to form a pressure-sensitive adhesive film having a thickness of 10 ⁇ m. Then, a silicone resin-coated polyethylene terephthalate (PET) film was laminated on the adhesive film to obtain a laminated film. The laminated film was aged at 40 ° C. for 3 days to obtain a surface protective film of Example B1 having "PET film (base film) / adhesive film / silicone resin coated PET film (cover film)".
- PET polyethylene terephthalate
- cover film cover film
- Examples B2 to B10 and Comparative Examples B1 to B7 In the same manner as in Example B1, the adhesive compositions of Examples A2 to A10 and Comparative Examples A1 to A7 were used to obtain surface protective films of Examples B2 to B10 and Comparative Examples B1 to B7.
- ⁇ Surface resistivity> The evaluation was performed in an environment of a temperature of 23 ° C. and a humidity of 50% RH.
- the cover film was peeled off from the surface protective film, and the surface resistivity ( ⁇ / ⁇ ) of the adhesive film was measured using a resistivity meter (“Hiresta-UX MCP-HT800 High resistivity meter” manufactured by Mitsubishi Electric Corporation).
- aE + b represents "a ⁇ 10 b ".
- the surface protective film was cut to obtain an evaluation film having a width of 25 mm and a length of 150 mm.
- the cover film was peeled off from the evaluation film, and the evaluation film was attached to the glass plate so that the surface on the adhesive film side was in contact with the surface of the degreased glass plate to prepare a measurement sample.
- the evaluation film was prepared using a tensile tester device (“Autograph AG-X / R” manufactured by Shimadzu Corporation) at room temperature (25 ° C), 180 ° direction, and peeling speed of 300 mm / min.
- the peel strength was measured by peeling with.
- the obtained peel strength was defined as the adhesive strength (N / 25 mm).
- a polarizing plate having an adhesive layer on one side (“Sumikaran (registered trademark)” manufactured by Sumitomo Chemical Co., Ltd.) is attached to a glass plate using a roller so that the surface of the polarizing plate on the adhesive layer side is in contact with the surface of the glass plate. I pasted them together. Then, the surface protective film was attached to the polarizing plate using a roller so that the adhesive film was in contact with the surface of the polarizing plate to obtain a laminate. The surface protective film was peeled off after storing the laminate in an environment of 85 ° C. and 85% RH for a period of 1 day, 3 days, 20 days, or 40 days. The state of contamination on the surface of the polarizing plate after peeling was visually observed.
- the surface protective films of Examples B1 to B10 all had a surface resistivity of 1.0 ⁇ 10 12 ⁇ / ⁇ or less, and had excellent antistatic properties.
- the surface protective films of Examples B1 and B2 were able to obtain excellent adhesiveness to the adherend, and were able to achieve both high antistatic property and high low contamination property.
- the surface protective films of Comparative Examples B1 to B3 did not exhibit excellent antistatic properties because the adhesive film did not contain the alkali metal salt (B) or the compound (C) represented by the formula (I). .. Further, the surface protective films of Comparative Examples B4, B6, and B7 were inferior in low stain resistance. It is presumed that one of the causes is that the alkylene glycol used in place of the alkali metal salt (B) and the compound (C) represented by the formula (I) caused minute cohesive failure of the adhesive film. .. Further, in Comparative Example B5, since calcium carbonate was not dissolved in the composition for the pressure-sensitive adhesive, the pressure-sensitive adhesive film could not be produced.
- the pressure-sensitive adhesive film formed by using the pressure-sensitive adhesive composition according to the embodiment of the present invention exhibits excellent adhesiveness, antistatic property, and low stain resistance, and the surface protective film provided with the pressure-sensitive adhesive film is an optical member or the like. It was suitable for protection of.
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Abstract
Description
(式中、Xは、それぞれ独立に、酸素原子又は窒素原子を表し、Rは、それぞれ独立に、水素原子、アルキル基、又はフルオロアルキル基を表す。)
本発明の実施形態である粘着剤用組成物は、(メタ)アクリルポリマー(A)、アルカリ金属塩(B)、及び式(1)で表される化合物(C)を含有する。粘着剤用組成物は、架橋剤(D)、各種の添加剤等の任意の成分を更に含有してもよい。
(メタ)アクリルポリマー(A)は、(メタ)アクリルモノマーに由来する構造単位を含むポリマーである。(メタ)アクリルモノマーは、分子内に少なくとも1つの(メタ)アクリロイル基を有する。本明細書において、「(メタ)アクリルモノマー」はアクリルモノマー及びメタクリルモノマーの総称であり、「(メタ)アクリロイル基」はアクリロイル基及びメタクリロイル基の総称である。
1/Tg=W1/Tg1+W2/Tg2+・・・+Wn/Tgn
(式中、Tgは(メタ)アクリルポリマー(A)のガラス転移温度(℃)であり、W1、W2、・・・、Wnは、それぞれ、全モノマーの質量を基準とする各モノマーの質量分率であり、Tg1、Tg2、・・・、Tgnは、それぞれ、各モノマーのホモポリマーのガラス転移温度である。この計算に用いるホモポリマーのガラス転移温度として、文献値を用いることができる。各種ホモポリマーのガラス転移温度は、例えば、三菱レイヨン株式会社のアクリルエステルカタログ(1997年度版)、及び、新高分子文庫7、「塗料用合成樹脂入門」高分子刊行会、北岡協三著に記載されている。
アルカリ金属塩(B)は、アルカリ金属イオンと対アニオンとを含む。粘着剤用組成物がアルカリ金属塩(B)を含むことにより、粘着フィルムに導電性が付与され、粘着フィルムが良好な帯電防止性を示すものとなると考えられる。アルカリ金属塩(B)は、アルカリ金属イオンとして、リチウムイオン、ナトリウムイオン、及びカリウムイオンからなる群から選択される少なくとも1種を含むことが好ましく、リチウムイオン及びナトリウムイオンからなる群から選択される少なくとも1種を含むことがより好ましく、リチウムイオンを含むことが更に好ましい。リチウムイオンを含む場合、より良好な帯電防止性が得られる。
粘着剤用組成物は、下記式(I)で表される化合物(C)を含有する。粘着フィルムにおいて、化合物(C)によりアルカリ金属塩(B)に含まれるアルカリ金属イオンの移動が促され、帯電防止性が高められると考えられる。
Xが酸素原子である場合、式(I)に含まれる-X-は-O-を表す。Xが窒素原子である場合、窒素原子には水素原子が結合してよく、式(I)に含まれる-X-は-NH-で表すことができる。
粘着剤用組成物は、架橋剤(D)を含有してもよい。架橋剤(D)は、例えば、イソシアネート化合物、エポキシ化合物、(メタ)アクリレート化合物、及び金属キレート化合物からなる群から選択される少なくとも1種を含むことが好ましい。加熱により架橋反応を進めることができることから、架橋剤(D)は、例えば、イソシアネート化合物及びエポキシ化合物からなる群から選択される少なくとも1種を含むことがより好ましく、イソシアネート化合物を含むことが更に好ましい。
粘着剤用組成物は、他の任意成分を含有してもよい。他の任意成分として、界面活性剤、可塑剤、充填剤、硬化遅延剤、加工助剤、老化防止剤、酸化防止剤等が挙げられる。粘着剤用組成物は、他の任意成分を、1種単独で含有しても、2種以上組み合わせて含有してもよい。
本発明の実施形態である粘着フィルムは、前記粘着剤用組成物を用いて得られるフィルムである。粘着フィルムにおいて、(メタ)アクリルポリマー(A)は、架橋されていてもよい。粘着フィルムの製造方法は特に限定されず、公知の製造方法でよい。粘着フィルムは、例えば、支持フィルムの表面に粘着剤用組成物の層を形成し、粘着剤用組成物の層を乾燥及び/又は硬化させることによって得ることができる。又は、粘着フィルムは、例えば、押し出し法により形成することができる。支持フィルム上に形成された粘着フィルムは、支持フィルムから剥離した後に使用してもよいし、支持フィルムから剥離せずに、粘着フィルムと支持フィルムとを有する積層体の状態で使用してもよい。
粘着フィルムを被着体に貼り付け、85℃85%RH(RH:相対湿度)の高温高湿条件に所定の時間にわたり静置後する。その後、粘着フィルムを被着体から剥離し、被着体への粘着剤の付着の有無を目視で確認する。「所定の時間」は、3日間、20日間、又は40日間とすることができる。
本発明の実施形態である表面保護フィルムは、前記粘着剤用組成物を用いて得られる粘着フィルムと、基材フィルムとを有する。表面保護フィルムは、カバーフィルム等の他の任意のフィルムを有してもよい。表面保護フィルムの例として、基材フィルムと、基材フィルムの一方の面上に設けられた粘着フィルムとを有する表面保護フィルム;基材フィルムと、基材フィルムの一方の面上に設けられた粘着フィルムと、粘着フィルムの基材フィルムとは反対側の面上に設けられたカバーフィルムとを有する表面保護フィルム等が挙げられる。
[実施例A1]
撹拌機、温度計、還流冷却器及び窒素導入管を備えた反応装置に、2-エチルヘキシルアクリレート90質量部、4-ヒドロキシブチルアクリレート10質量部、溶剤として酢酸エチル50質量部、重合開始剤としてアゾビスイソブチロニトリル0.1質量部を加えた。次いで、窒素ガスを導入して、1時間かけて反応系内の空気を窒素ガスで置換した。その後、75℃で7時間反応させ、重量平均分子量50万の(メタ)アクリルポリマー(A-1)の溶液を得た。
検出器:RI(示差屈折計)
溶媒:純正1級THF(テトラヒドロフラン)
ガードカラム:TSK-guard column Super MP(HZ)-H(1本)
ガードカラムサイズ:4.6mm(ID)×20mm
カラム:東ソー株式会社製 TSK-GEL Super Multipore HZ-H(3本連結)
カラムサイズ:4.6mm(ID)×150mm
温度:40℃
試料濃度:0.01g/5mL
注入量:10μL
流量:0.35mL/min
表1に記載のモノマーを用いた以外は実施例A1と同様にして(メタ)アクリルポリマー(A-2)~(A-4)の溶液を得た。次いで、表2及び3に記載の成分を用いた以外は実施例A1と同様にして、実施例A2~A10及び比較例A1~A7の粘着剤用組成物を得た。(メタ)アクリルポリマー(A-5)は、綜研化学株式会社製「SKダイン(登録商標)1499M」である。表1~3には、各成分の固形分の量(質量部)を示した。
[実施例B1]
実施例A1の粘着剤用組成物を、ポリエチレンテレフタレート(PET)フィルムの上に塗布し、110℃で2分間加熱し、乾燥及び硬化させることによって、厚さが10μmである粘着フィルムを形成した。その後、シリコーン樹脂コートされたポリエチレンテレフタレート(PET)フィルムを、粘着フィルムの上にラミネートし、積層フィルムを得た。積層フィルムを40℃で3日間エージングし、「PETフィルム(基材フィルム)/粘着フィルム/シリコーン樹脂コートされたPETフィルム(カバーフィルム)」を有する実施例B1の表面保護フィルムを得た。
実施例B1と同様にして、実施例A2~A10及び比較例A1~A7の粘着剤用組成物を用い、実施例B2~B10及び比較例B1~B7の表面保護フィルムを得た。
実施例B1~B10及び比較例B1~B7の表面保護フィルムについて、粘着フィルムの表面抵抗率、粘着力、及び低汚染性を評価した。評価結果を表5及び6に示す。
評価は、温度23℃湿度50%RHの環境下で行った。表面保護フィルムからカバーフィルムを剥離し、抵抗率計(三菱電機株式会社製「Hiresta-UX MCP-HT800高抵抗率計」)を用いて粘着フィルムの表面抵抗率(Ω/□)を測定した。表5及び6中、「aE+b」は「a×10b」を表す。
表面保護フィルムを切断し、幅25mm、長さ150mmの評価用フィルムを得た。評価用フィルムからカバーフィルムを剥がし、粘着フィルム側の面が脱脂したガラス板の表面に接するように、評価用フィルムをガラス板に貼り合わせ、測定試料とした。測定試料から、評価用フィルムを、引張試験機装置(株式会社島津製作所製「オートグラフAG-X/R」)を用いて、室温(25℃)、180°方向、剥離速度300mm/minの条件で剥がして、剥離強度を測定した。得られた剥離強度を粘着力(N/25mm)とした。
片面に粘着層を有する偏光板(住友化学株式会社製「スミカラン(登録商標)」)を、ガラス板に、偏光板の粘着層側の面がガラス板の表面に接するように、ローラーを用いて貼り合わせた。その後、表面保護フィルムを、偏光板に、粘着フィルムが偏光板の表面に接するように、ローラーを用いて貼り合わせ、積層体を得た。積層体を85℃85%RHの環境下で、1日間、3日間、20日間、又は40日間の期間にわたって保管した後に、表面保護フィルムを剥がした。剥離後の偏光板の表面の汚染状態を目視にて観察した。
20日間保管及び40日間保管のいずれにおいても「汚染なし」の場合
5点
20日間保管において「汚染なし」だが40日間保管において「わずかに汚染あり」の場合 4点
3日間保管において「汚染なし」だが20日間保管において「わずかに汚染あり」の場合 3点
20日間保管において「汚染あり」の場合 2点
3日間保管において「汚染あり」の場合 1点
2 カバーフィルム
3 粘着フィルム
4 基材フィルム
Claims (5)
- 架橋剤(D)を更に含有する、請求項1に記載の粘着剤用組成物。
- 前記(メタ)アクリルポリマー(A)が、アルキル(メタ)アクリレートモノマーに由来する構造単位、及び、ヒドロキシル基又はカルボキシル基を有する(メタ)アクリルモノマーに由来する構造単位を含む、請求項1又は2に記載の粘着剤用組成物。
- 請求項1~3のいずれかに記載の粘着剤用組成物を用いて得られる、粘着フィルム。
- 請求項1~3のいずれかに記載の粘着剤用組成物を用いて得られる粘着フィルムと、基材フィルムとを有する、表面保護フィルム。
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| CN202080031399.3A CN113767156B (zh) | 2019-04-26 | 2020-03-24 | 粘合剂用组合物、粘合膜和表面保护膜 |
| KR1020217034692A KR20220002322A (ko) | 2019-04-26 | 2020-03-24 | 점착제용 조성물, 점착 필름 및 표면 보호 필름 |
| CN202311460704.2A CN117511453A (zh) | 2019-04-26 | 2020-03-24 | 粘合剂用组合物、粘合膜和表面保护膜 |
| KR1020267001188A KR20260016008A (ko) | 2019-04-26 | 2020-03-24 | 점착제용 조성물, 점착 필름 및 표면 보호 필름 |
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| JP2019086702A JP2020183461A (ja) | 2019-04-26 | 2019-04-26 | 粘着剤用組成物、粘着フィルム、及び表面保護フィルム |
| JP2019-086702 | 2019-04-26 |
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| JP5503926B2 (ja) * | 2009-08-31 | 2014-05-28 | ビッグテクノス株式会社 | 電気剥離性粘着製品及びその剥離方法 |
| JP5544800B2 (ja) | 2009-09-17 | 2014-07-09 | サイデン化学株式会社 | 表面保護フィルム |
| JP5885286B2 (ja) * | 2011-03-29 | 2016-03-15 | 日東電工株式会社 | 粘着シートおよびその利用 |
| JP2013163783A (ja) * | 2012-02-13 | 2013-08-22 | Fujimori Kogyo Co Ltd | 粘着剤組成物、粘着フィルム及び表面保護フィルム |
| KR101887570B1 (ko) * | 2012-09-04 | 2018-08-10 | 동우 화인켐 주식회사 | 점착제 조성물 |
| JP7020606B2 (ja) * | 2017-08-10 | 2022-02-16 | 日本カーバイド工業株式会社 | 保護フィルム用粘着剤組成物及び保護フィルム |
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- 2020-03-24 CN CN202080031399.3A patent/CN113767156B/zh active Active
- 2020-03-24 CN CN202311460704.2A patent/CN117511453A/zh active Pending
- 2020-03-24 WO PCT/JP2020/013054 patent/WO2020217820A1/ja not_active Ceased
- 2020-03-24 KR KR1020267001188A patent/KR20260016008A/ko active Pending
- 2020-03-24 KR KR1020217034692A patent/KR20220002322A/ko not_active Ceased
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| JPH07282846A (ja) * | 1994-04-07 | 1995-10-27 | Matsushita Electric Ind Co Ltd | 非水電解質電池 |
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| Publication number | Publication date |
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| KR20260016008A (ko) | 2026-02-03 |
| TWI875748B (zh) | 2025-03-11 |
| KR20220002322A (ko) | 2022-01-06 |
| JP2020183461A (ja) | 2020-11-12 |
| CN113767156A (zh) | 2021-12-07 |
| JP2023164662A (ja) | 2023-11-10 |
| CN117511453A (zh) | 2024-02-06 |
| CN113767156B (zh) | 2023-11-28 |
| TW202106836A (zh) | 2021-02-16 |
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