WO2016027787A1 - 粘着剤組成物、これを架橋させてなる粘着剤、マスキングフィルム用粘着剤、耐熱粘着フィルム用粘着剤、マスキング用耐熱粘着フィルム、およびその使用方法 - Google Patents
粘着剤組成物、これを架橋させてなる粘着剤、マスキングフィルム用粘着剤、耐熱粘着フィルム用粘着剤、マスキング用耐熱粘着フィルム、およびその使用方法 Download PDFInfo
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- WO2016027787A1 WO2016027787A1 PCT/JP2015/073056 JP2015073056W WO2016027787A1 WO 2016027787 A1 WO2016027787 A1 WO 2016027787A1 JP 2015073056 W JP2015073056 W JP 2015073056W WO 2016027787 A1 WO2016027787 A1 WO 2016027787A1
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- pressure
- sensitive adhesive
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- masking
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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
-
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- 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
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/31—Applications of adhesives in processes or use of adhesives in the form of films or foils as a masking tape for painting
Definitions
- the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive obtained by crosslinking the same, a pressure-sensitive adhesive for masking film, a pressure-sensitive adhesive for heat-resistant pressure-sensitive adhesive film, a heat-resistant pressure-sensitive adhesive film for masking, and a method for using the same.
- the pressure-sensitive adhesive composition can be used for a heat-resistant pressure-sensitive adhesive film for masking that hardly causes contamination when peeled off from an adherend and can be peeled off with a small force, a pressure-sensitive adhesive formed by crosslinking this, Masking film pressure-sensitive adhesive made of pressure-sensitive adhesive, pressure-sensitive adhesive for heat-resistant pressure-sensitive adhesive film made of the pressure-sensitive adhesive, heat-resistant pressure-sensitive adhesive film for masking having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive on the film, and use of the heat-resistant pressure-sensitive adhesive film for masking Regarding the method.
- Flexible printed wiring (FPC) substrates are used in information terminal electronic devices such as mobile phones.
- FPC Flexible printed wiring
- thinning of laminates including FPC substrates has become possible due to higher circuit performance and smaller and lighter electronic devices.
- Miniaturization is progressing.
- the strength of the laminated plate is reduced and is easily damaged, it is necessary to protect the laminated plate with a protective film during the manufacturing process in order to prevent the damage.
- the adhesive layer of the protective film may adhere to the laminated board, and the laminated board may be damaged when the protective film is peeled off or may be contaminated by adhesive residue.
- adhesive force may fall under high temperature conditions and a float may be produced, there also exists a problem which cannot fully exhibit protective ability as a protective film.
- an ITO transparent electrode layer that is a constituent member of a touch panel used for a portable information terminal such as a smartphone
- an ITO transparent electrode layer is formed on a laminated plate, and then a protective film is pasted.
- An annealing process step of heating under a condition of 150 to 200 ° C. in a state in which is attached is included. Since it is exposed to a high temperature during this manufacturing process, the adhesive layer of the protective film adheres to the laminate, and the ITO transparent electrode layer may be damaged when the protective film is peeled off, or contamination due to adhesive residue may occur. Moreover, since adhesive force may fall under high temperature conditions and a float may be produced, there also exists a problem which cannot fully exhibit protective ability as a protective film.
- Patent Document 1 discloses a hydroxyl group-containing acrylic resin having a weight average molecular weight of 450,000 to 1,500,000 and an isocyanate-based crosslinking agent, and an isocyanate in the isocyanate-based crosslinking agent relative to the hydroxyl group amount in the hydroxyl group-containing acrylic resin. In the range where the group amount is 0.6 to 1.6 times (molar ratio), the hydroxyl group-containing acrylic resin and the isocyanate-based crosslinking agent and the non-crosslinking agent are further added to 100 parts by weight of the hydroxyl group-containing acrylic resin.
- a pressure-sensitive adhesive composition containing 3 to 20 parts by weight of an ester compound which is reactive and has a formula weight or a number average molecular weight of 300 to 1500 is disclosed.
- Patent Document 2 discloses a pressure-sensitive adhesive composition for a heat-resistant fine-adhesive film or sheet that is laminated to a film or sheet such as an FPC base material and reinforces the film or sheet.
- a heat-resistant slightly pressure-sensitive adhesive composition characterized in that an acrylic resin and an isocyanate resin and a metal chelating agent are blended is disclosed.
- Patent Document 1 since a low molecular weight compound having a number average molecular weight of 300 to 1500 is used, the compound itself may be a causative substance of the adherend, and the pressure-sensitive adhesive The layer may cause a decrease in cohesive force under high temperature conditions, and the adhesive may remain on the adherend.
- the present invention also provides a pressure-sensitive adhesive obtained by crosslinking this pressure-sensitive adhesive composition, a pressure-sensitive adhesive for masking film comprising the pressure-sensitive adhesive, a pressure-sensitive adhesive for heat-resistant pressure-sensitive adhesive film comprising the pressure-sensitive adhesive, and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive.
- Another object of the present invention is to provide a heat-resistant adhesive film for masking on a film and a method for using the heat-resistant adhesive film for masking.
- the gist of the present invention includes an acrylic resin (A) having a structural unit derived from the polyoxyethylene structure-containing monomer (a1) and a structural unit derived from the (meth) acrylic acid alkyl ester monomer (a2).
- the present invention relates to a pressure-sensitive adhesive composition, characterized in that the content of structural units derived from the polyoxyethylene structure-containing monomer (a1) is 10 to 45% by weight and does not contain an antistatic agent. Is.
- the gist of the present invention is that an acrylic resin (A) obtained by copolymerizing a polyoxyethylene structure-containing monomer (a1) and a copolymerization component containing a (meth) acrylic acid alkyl ester monomer (a2). In which the content of the polyoxyethylene structure-containing monomer (a1) in the copolymer component is 10 to 45% by weight. is there.
- the gist of the present invention is that the pressure-sensitive adhesive composition of the present invention is crosslinked, the pressure-sensitive adhesive for masking film characterized by comprising the pressure-sensitive adhesive of the present invention, and the pressure-sensitive adhesive of the present invention.
- Also related to a method for using a heat-resistant pressure-sensitive adhesive film for masking characterized in that the heat-resistant pressure-sensitive adhesive film for masking is peeled off from the surface of the adherend after being attached to the surface of the adherend and subjected to a heating step of 100 ° C. or higher. It is.
- the “adhesive film” in the present invention conceptually includes an adhesive sheet, an adhesive film, and an adhesive tape.
- the pressure-sensitive adhesive composition of the present invention is a copolymer of an acrylic resin containing a specific amount of a structural unit derived from a polyoxyethylene structure-containing monomer, for example, a copolymer component containing a specific amount of a monomer component containing a polyoxyethylene structure.
- the contact area does not increase because there are almost no gaps. Due to this effect, even after the masking heat-resistant adhesive film affixed to the adherend is exposed to a high temperature, adherend adherence such as adhesive residue is less likely to occur when the masking heat-resistant adhesive film is peeled off. With this, the masking heat-resistant adhesive film can be peeled off.
- the pressure-sensitive adhesive composition of the present invention and a pressure-sensitive adhesive obtained by crosslinking the same, it is difficult to cause contamination when peeled from an adherend after use under high temperature conditions, and can be peeled off with a small force.
- a heat-resistant adhesive film for masking can be produced.
- (meth) acryl means acryl or methacryl
- (meth) acryloyl means acryloyl or methacryloyl
- (meth) acrylate means acrylate or methacrylate.
- the pressure-sensitive adhesive composition of the present invention comprises an acrylic resin (A).
- the acrylic resin (A) used in the present invention has a structural unit derived from the polyoxyethylene structure-containing monomer (a1) and a structural unit derived from the (meth) acrylic acid alkyl ester monomer (a2). For example, it is obtained by copolymerizing a copolymer component containing a polyoxyethylene structure-containing monomer (a1) and a (meth) acrylic acid alkyl ester monomer (a2).
- the acrylic resin (A) may further have a structural unit appropriately selected from the structural unit derived from the functional group-containing monomer (a3) and the structural unit derived from the other copolymerizable monomer (a4).
- a monomer appropriately selected from the functional group-containing monomer (a3) and the other copolymerizable monomer (a4) can be used.
- the polyoxyethylene structure-containing monomer (a1) used in the present invention is a monomer having two or more oxyethylene structures.
- the number of repeating units of the oxyethylene chain of the polyoxyethylene structure-containing monomer (a1) is usually 2 or more, preferably 2 to 20, particularly preferably 2 to 15, and more preferably 2 to 10. If the number of repeating units is too small, the conformability to the adherend tends to be poor, and if it is too large, the adherend contamination after heating tends to increase.
- the polyoxyethylene structure-containing monomer (a1) is preferably a polyoxyethylene structure-containing (meth) acrylate monomer from the viewpoint of copolymerization.
- a polyoxyethylene structure-containing (meth) acrylate monomer from the viewpoint of copolymerization.
- examples of the polyoxyethylene structure-containing monomer (a1) include a polyoxyethylene structure-containing (meth) acrylate represented by the following general formula (1).
- X is an ethylene group
- Y is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group
- R 1 is a hydrogen atom or a methyl group
- n is an integer of 2 or more.
- X in the general formula (1) is an ethylene group.
- Y in the general formula (1) is any one of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group.
- a hydrogen atom, an alkyl group, and an aryl group are preferable, a hydrogen atom, an alkyl group, and a phenyl group are particularly preferable, and an alkyl group is more preferable.
- the alkyl group is preferably an alkyl group having a relatively short carbon number, specifically an alkyl group usually having 1 to 15 carbon atoms, preferably 1 to 10, and particularly preferably 1 to 6. More specifically, Y in the general formula (1) is preferably a methyl group, an ethyl group, or a propyl group, and particularly preferably a methyl group.
- aryl group those having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms are usually used, and specific examples include phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, etc. Of these, a phenyl group is preferred.
- aralkyl group those having 7 to 20 carbon atoms, preferably 7 to 15 carbon atoms are usually used, and specific examples include a benzyl group.
- the alkyl group, aryl group, and aralkyl group may have a substituent.
- the substituent is usually a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, a hydroxyl group, an alkoxy group.
- a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, a hydroxyl group, an alkoxy group.
- R 1 in the general formula (1) is a hydrogen atom or a methyl group.
- n is an integer of 2 or more, preferably 2 to 20, particularly preferably 2 to 15, and more preferably 2 to 10.
- Preferred examples of the polyoxyethylene structure-containing monomer (a1) include methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate.
- the content of the polyoxyethylene structure-containing monomer (a1) in the copolymerization component is usually 10 to 45% by weight, preferably 10 to 40% by weight, particularly preferably 15 to 35% by weight, and more preferably 15%. ⁇ 30% by weight. If the content is too small, the adhesive strength after the heating step tends to be high, and if it is too large, adherend contamination after the heating step tends to increase.
- the content of the structural unit derived from the polyoxyethylene structure-containing monomer (a1) in the acrylic resin (A) can be calculated by measuring with 1 H-NMR.
- the (meth) acrylic acid alkyl ester monomer (a2) used in the present invention is a (meth) acrylate having an aliphatic or alicyclic alkyl ester.
- the number of carbon atoms in the alkyl ester is usually 1-20, preferably 1-12, particularly preferably 1-6. When there are too many carbons, there exists a tendency for the adherend contamination after a heating process to increase.
- Preferred (meth) acrylic acid alkyl ester monomers (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and tert-butyl (meth). Examples thereof include acrylate, n-propyl (meth) acrylate, and n-hexyl (meth) acrylate. These can be used alone or in combination of two or more.
- the content of the (meth) acrylic acid alkyl ester monomer (a2) in the copolymerization component is usually 40 to 90% by weight, preferably 45 to 85% by weight, particularly preferably 50 to 80% by weight. .
- the content of the structural unit derived from the (meth) acrylic acid alkyl ester monomer (a2) in the acrylic resin (A) can be calculated by measuring with 1 H-NMR.
- the content of the (meth) acrylic acid alkyl ester monomer (a2-1) having an alkyl group having 1 to 6 carbon atoms is 80% by weight or more. It is preferable that it is excellent in adherend adherence after the heating step, particularly preferably 85% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more.
- the functional group-containing monomer (a3) may be any monomer containing a functional group that can become a crosslinking point by reacting with the below-mentioned crosslinking agent (B).
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meta )
- Acrylic acid hydroxyalkyl esters such as acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate and other caprolactone-modified monomers, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate and other oxyalkylene-modified monomers, other 2-acrylic Primary hydroxyl group-containing monomers such as leuoxyethyl-2-hydroxyethylphthalic acid; Secondary hydroxyl group-containing monomers such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 3-chloro-2-hydroxypropyl (meth) acrylate; Examples thereof include
- hydroxyl-containing monomer used by this invention it is also preferable to use a thing with the content rate of di (meth) acrylate which is an impurity 0.5% or less, and also 0.2% or less, especially 0 It is preferable to use a material of 1% or less.
- carboxyl group-containing monomer examples include (meth) acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, and cinnamon.
- An acid etc. are mentioned, Especially, (meth) acrylic acid is used preferably.
- amino group-containing monomer examples include t-butylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like.
- acetoacetyl group-containing monomer examples include 2- (acetoacetoxy) ethyl (meth) acrylate and allyl acetoacetate.
- isocyanate group-containing monomer examples include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.
- Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate, allyl glycidyl (meth) acrylate, and the like.
- a hydroxyl group-containing monomer and / or a carboxyl group-containing monomer are preferably used in that a crosslinking reaction can be efficiently performed.
- These functional group-containing monomers (a3) may be used alone or in combination of two or more.
- the content of the functional group-containing monomer (a3) in the copolymerization component is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 15% by weight. If the content is too small, the degree of cross-linking tends to decrease and adherend contamination tends to increase. If it is too large, the adhesive strength immediately after application tends to be too high.
- the content of the structural unit derived from the functional group-containing monomer (a3) in the acrylic resin (A) can be calculated by measuring with 1 H-NMR.
- Examples of the other copolymerizable monomer (a4) that may be used in the present invention include ethoxymethyl (meth) acrylamide, n-butoxymethyl (meth) acrylamide, (meth) acryloylmorpholine, dimethyl (meth) acrylamide, (Meth) acrylamide monomers such as diethyl (meth) acrylamide, (meth) acrylamide N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide; Aminoalkyl (meth) acrylate monomers such as aminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate ; One fragrance such as phenyl (meth) acrylate, benzyl (meth
- a monomer containing a ring Biphenyloxy structure-containing (meth) acrylic acid ester monomers such as biphenyloxyethyl (meth) acrylate; Alkoxy such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
- Biphenyloxy structure-containing (meth) acrylic acid ester monomers such as biphenyloxyethyl (meth) acrylate
- Alkoxy such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth
- a monomer containing a group or an oxyalkylene group Acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride Methyl vinyl ketone, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, and the like.
- (meth) acrylamide monomers are preferred in that adherend contamination after the heating step is reduced. These can be used alone or in combination of two or more.
- the content of the other copolymerizable monomer (a4) in the copolymerization component is usually 0 to 40% by weight, preferably 0.001 to 30% by weight, particularly preferably 0.01 to 25% by weight. is there. When there is too much content, there exists a tendency for an adhesive characteristic to fall easily.
- the content of the structural unit derived from the other copolymerizable monomer (a4) in the acrylic resin (A) can be calculated by measuring with 1 H-NMR.
- the polyoxyethylene structure-containing monomer (a1), the (meth) acrylic acid alkyl ester monomer (a2), the functional group-containing monomer (a3), and other copolymerizable monomers (a4) as necessary are copolymerized.
- An acrylic resin (A) having a structural unit derived from the monomer (a3) and a structural unit derived from another copolymerizable monomer (a4) can be produced.
- the acrylic resin (A) conventionally known methods such as solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization can be employed.
- the organic solvent the polyoxyethylene structure-containing monomer (a1), the (meth) acrylic acid alkyl ester monomer (a2), the functional group-containing monomer (a3), and other copolymerizable monomers (a4)
- the above polymerizable monomer and polymerization initiator azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, etc.
- polymerization is carried out at reflux or at 50 to 90 ° C. for 2 to 20 hours.
- the content of the structural unit derived from the polyoxyethylene structure-containing monomer (a1) in the acrylic resin (A) obtained above is 10 to 45% by weight, preferably 10 to 40% by weight, particularly preferably 15 to It is 35% by weight, more preferably 15 to 30% by weight. If the content is too small, the adhesive strength after the heating step tends to be high, and if it is too large, adherend contamination after the heating step tends to increase.
- the content of the structural unit derived from the (meth) acrylic acid alkyl ester monomer (a2) in the acrylic resin (A) is usually 40 to 90% by weight, preferably 45 to 85% by weight, particularly preferably 50%. ⁇ 80 wt%. When the content is too small, adherend contamination after the heating step tends to increase, and when too large, the adhesive strength after the heating step tends to be too high.
- the content of the structural unit derived from the functional group-containing monomer (a3) in the acrylic resin (A) is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 15% by weight. If the content is too small, the degree of cross-linking tends to decrease and adherend contamination tends to increase. If it is too large, the adhesive strength immediately after application tends to be too high.
- the content of the structural unit derived from the other copolymerizable monomer (a4) in the acrylic resin (A) is usually 0 to 40% by weight, preferably 0.001 to 30% by weight, particularly preferably 0.8. 01 to 25% by weight. When there is too much content, there exists a tendency for an adhesive characteristic to fall easily.
- the weight average molecular weight of the acrylic resin (A) is usually 100,000 to 2.5 million, preferably 200,000 to 2,200,000, particularly preferably 400,000 to 2,000,000. If the weight average molecular weight is too low, the heat resistance of the pressure-sensitive adhesive layer tends to decrease and the adherend contamination tends to increase. If it is too high, a large amount of dilution solvent is required, which is disadvantageous in terms of coating properties and cost. Tend to be.
- the degree of dispersion (weight average molecular weight / number average molecular weight) of the acrylic resin (A) is, for example, usually 20 or less, preferably 15 or less, particularly preferably 10 or less, and the lower limit is usually 1.1. is there. If the degree of dispersion is too high, the heat resistance of the pressure-sensitive adhesive layer tends to decrease, and foaming and the like tend to occur.
- said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, and it is a column in a high performance liquid chromatography (The Japan Waters company, "Waters 2695 (main body)” and “Waters 2414 (detector)”).
- Shodex GPC KF-806L exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece
- filler material styrene-divinylbenzene copolymer
- the particle diameter is measured by using three series of 10 ⁇ m), and the same method can be used for the number average molecular weight.
- the degree of dispersion is determined from the weight average molecular weight and the number average molecular weight. In the measurement, the polymer may be derivatized or the type of the eluent may be appropriately changed.
- the glass transition temperature of the acrylic resin (A) is usually ⁇ 70 to 0 ° C., preferably ⁇ 65 to ⁇ 5 ° C., particularly preferably ⁇ 60 to ⁇ 10 ° C. If the glass transition temperature is too high, the adhesive strength after the heating step tends to be high, and if the glass transition temperature is too low, the heat resistance tends to decrease and adherend contamination tends to increase.
- the glass transition temperature is calculated from the following Fox equation.
- Tg Glass transition temperature of copolymer (K)
- Tga Glass transition temperature (K) of homopolymer of monomer a
- Wa weight fraction of monomer a
- Tgb glass transition temperature (K) of homopolymer of monomer b
- Wb weight fraction of monomer b
- Tgn glass transition temperature (K) of homopolymer of monomer n
- the pressure-sensitive adhesive composition of the present invention contains the acrylic resin (A) as an essential component, and the composition is crosslinked as it is or by adding the crosslinking agent (B) to the composition. Can be used as an adhesive.
- the pressure-sensitive adhesive composition is crosslinked, it is preferable that the pressure-sensitive adhesive composition further contains a crosslinking agent (B).
- crosslinking agent (B) examples include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, melamine crosslinking agents, aldehyde crosslinking agents, and amine crosslinking agents.
- an isocyanate-based crosslinking agent is preferably used in terms of improving the adhesion of the heat-resistant adhesive film to the base material and the reactivity with the base polymer.
- isocyanate crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hexamethylene.
- isocyanurate of hexamethylene diisocyanate, 2,4-tolylene diisocyanate and / or adduct of 2,6-tolylene diisocyanate and trimethylolpropane 2,4-tolylene diisocyanate and An isocyanurate of 2,6-tolylene diisocyanate and an adduct of tetramethylxylylene diisocyanate and trimethylolpropane are preferred.
- epoxy-based crosslinking agent examples include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexanediol diglycidyl ether.
- Trimethylolpropane triglycidyl ether Trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether, 1,3′-bis (N, N-diglycidylaminomethyl) cyclohexane, N , N, N ′, N′-tetraglycidyl-m-xylenediamine and the like.
- aziridine-based crosslinking agent examples include tetramethylolmethane-tri- ⁇ -aziridinylpropionate, trimethylolpropane-tri- ⁇ -aziridinylpropionate, N, N′-diphenylmethane-4,4.
- oxazoline-based crosslinking agent examples include 2,2′-bis (2-oxazoline), 1,2-bis (2-oxazolin-2-yl) ethane, and 1,4-bis (2-oxazoline-2- Yl) butane, 1,8-bis (2-oxazolin-2-yl) butane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazolin-2-yl) Aliphatic or aromatic bisoxazoline compounds such as benzene and 1,3-bis (2-oxazolin-2-yl) benzene, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- - addition-polymerizable o
- Examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexaptoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, and melamine resin. .
- aldehyde-based crosslinking agent examples include glyoxal, malondialdehyde, succindialdehyde, maleindialdehyde, glutardialdehyde, formaldehyde, acetaldehyde, benzaldehyde and the like.
- amine-based crosslinking agent examples include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetraamine, diethylenetriamine, triethyltetraamine, isophoronediamine, amino resin, and polyamide.
- cross-linking agents (B) may be used alone or in combination of two or more.
- the content of the crosslinking agent (B) is usually 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, particularly 100 parts by weight of the acrylic resin (A).
- the amount is preferably 1 to 15 parts by weight. If the amount of the crosslinking agent (B) is too small, the cohesive strength of the pressure-sensitive adhesive tends to be reduced, causing adhesive residue. If the amount is too large, the pressure-sensitive adhesive is excessively cross-linked and the pressure-sensitive adhesive strength is reduced. There is a tendency to float between the kimono.
- the crosslinking reaction can be performed by irradiating active energy rays.
- polyfunctional (meth) acrylate examples include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, penta Trifunctional or higher functional (meth) such as erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyglycidyl ether poly (meth) acrylate, etc. ) Acrylate is preferred.
- the pressure-sensitive adhesive composition of the present invention is characterized by not containing an antistatic agent.
- ⁇ does not contain an antistatic agent '' is usually one that does not contain an antistatic agent at all, but may be contained to the extent that the adhesive composition does not have antistatic performance,
- the content of the antistatic agent in the pressure-sensitive adhesive composition is preferably 0.1% by weight or less, particularly preferably 0.05% by weight or less, more preferably 0.01% by weight or less. Good.
- antistatic agents examples include cationic antistatic agents of quaternary ammonium salts such as imidazolium salts and tetraalkylammonium sulfonates; addition of aliphatic sulfonates, higher alcohol sulfates, and higher alcohol alkylene oxides.
- Anionic antistatic agents such as sulfuric acid ester salts, higher alcohol phosphate salts, higher alcohol alcohol alkylene oxide adduct phosphate salts; potassium bis (fluorosulfonyl) imide, lithium bis (trifluorosulfonyl) imide and lithium chloride
- Alkali metal salts such as alkaline earth metal salts, higher alcohol alkylene oxide adducts, polyalkylene glycol fatty acid esters and the like.
- the pressure-sensitive adhesive composition of the present invention is an antioxidant, a plasticizer, a filler, a pigment, a diluent, an anti-aging agent, an ultraviolet absorber, an ultraviolet stabilizer, and a tackifying resin as long as the effects of the present invention are not impaired.
- Etc. may be further contained, and these additives may be used alone or in combination of two or more.
- the antioxidant is effective for maintaining the stability of the pressure-sensitive adhesive layer.
- the content when the antioxidant is blended is not particularly limited, but is preferably 0.01 to 5% by weight.
- a small amount of impurities contained in the raw materials for producing the constituent components of the pressure-sensitive adhesive composition may be contained.
- the pressure-sensitive adhesive composition of the present invention is preferably mainly composed of an acrylic resin (A).
- “main component” means that the acrylic resin (A) is usually contained in an amount of 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more based on the total amount of the pressure-sensitive adhesive composition. It means to do.
- the upper limit is usually 99.9% by weight.
- the pressure-sensitive adhesive composition of the present invention does not substantially contain an acid, whereby corrosion of an adherend such as a metal can be reduced.
- substantially free of acid specifically means that the acid value is preferably 5 mgKOH / g or less, particularly preferably 1 mgKOH / g or less, more preferably 0.1 mgKOH / g or less. means.
- the gel fraction of the pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition of the present invention is usually 40 to 100%, preferably 60 to 100%, particularly preferably 80 to 100%, more preferably 90 to 100%, Particularly preferred is 97 to 100%. If the gel fraction is too low, the cohesive force of the pressure-sensitive adhesive is lowered, and adhesive residue is generated, which tends to cause adherend contamination.
- the adjustment of the gel fraction of the pressure-sensitive adhesive to the above range can be achieved by adjusting the type and amount of the crosslinking agent, adjusting the composition ratio of hydroxyl groups in the composition, and the like. Moreover, since the gel fraction changes with each interaction, the ratio between the crosslinking agent and the functional group amount needs to be balanced.
- the gel fraction is a measure of the degree of crosslinking, and is calculated, for example, by the following method. That is, a pressure-sensitive adhesive sheet (not provided with a separator) in which a pressure-sensitive adhesive layer is formed on a polymer sheet (for example, polyethylene terephthalate film or the like) as a base material is wrapped with a 200-mesh SUS wire mesh, and 23 in toluene. The weight percentage of the insoluble pressure-sensitive adhesive component immersed in the wire mesh at 24 ° C. for 24 hours is defined as the gel fraction. However, the weight of the substrate is subtracted.
- the gel fraction after heat-treating the pressure-sensitive adhesive composition at 180 ° C. for 5 minutes is usually 30% to 100%, preferably Is 40 to 100%, particularly preferably 50 to 100%, and the gel fraction after heat treatment at 180 ° C. for 1 hour is usually 70% to 100%, preferably 80 to 100%, particularly Preferably it is 90 to 100%. If the gel fraction after heat treatment is too low, the cohesive force of the pressure-sensitive adhesive under superheated condition will be reduced, and adhesive residue will be generated, which tends to cause adherend contamination.
- a masking film and a heat-resistant adhesive film are prepared by preparing a pressure-sensitive adhesive for a masking film or a heat-resistant adhesive film from the above-mentioned pressure-sensitive adhesive composition, and forming a pressure-sensitive adhesive layer on the base film.
- a heat-resistant adhesive film for masking (hereinafter sometimes collectively referred to as an adhesive film) can be obtained.
- the adhesive which comprises an adhesive layer may be the said adhesive composition as it is, and the thing bridge
- the base material on which the pressure-sensitive adhesive layer is laminated examples include a single layer or laminated film made of metal, polyester resin, polyfluoroethylene resin, polyimide and derivatives thereof, epoxy resin, and the like.
- the heat-resistant adhesive film or the heat-resistant adhesive film for masking it is preferable to further provide a release film on the surface of the pressure-sensitive adhesive layer opposite to the base material.
- the release film is peeled off and used.
- a silicon release film, an olefin release film, a fluorine release film, a long-chain alkyl release film, and an alkyd release film can be used.
- the method of cross-linking the pressure-sensitive adhesive composition of the present invention containing the cross-linking agent (B) when producing the masking film, heat-resistant pressure-sensitive adhesive film or heat-resistant pressure-sensitive adhesive film for masking [1] After applying and drying the adhesive composition, a method of pasting the release film and performing an aging treatment, [2] Applying the adhesive composition on the release film, drying, and pasting the substrate
- the aging process can be performed.
- the method [2] is preferable from the viewpoint of not damaging the substrate, workability and stable production.
- the aging treatment of the pressure-sensitive adhesive film imparted with heat resistance usually requires aging at a high temperature for a long time, but in the present invention, by using aminoalkyl (meth) acrylamide, The aging process can be completed in a short time.
- the aging treatment is carried out to balance the physical properties of the adhesive.
- the temperature is usually 0 to 150 ° C., preferably 10 to 100 ° C., particularly preferably 20 to 80 ° C.
- the time is Usually, it is 30 days or less, preferably 14 days or less, particularly preferably 7 days or less. Specifically, it can be carried out under conditions such as 23 ° C. for 3 to 10 days, 40 ° C. for 1 to 7 days, and the like. .
- the pressure-sensitive adhesive composition is preferably diluted with a solvent, and the dilution concentration is preferably 5 to 60% by weight, particularly preferably 10 to 30% by weight.
- the solvent is not particularly limited as long as it dissolves the pressure-sensitive adhesive composition.
- ester solvents such as methyl acetate, ethyl acetate, methyl acetoacetate, and ethyl acetoacetate; acetone, methyl ethyl ketone, A ketone solvent such as methyl isobutyl ketone; an aromatic solvent such as toluene and xylene; and an alcohol solvent such as methanol, ethanol and propyl alcohol can be used.
- ester solvents such as methyl acetate, ethyl acetate, methyl acetoacetate, and ethyl acetoacetate
- acetone methyl ethyl ketone
- a ketone solvent such as methyl isobutyl ketone
- the application of the pressure-sensitive adhesive composition can be performed by a conventional method such as roll coating, die coating, gravure coating, comma coating, screen printing, or the like.
- the thickness of the pressure-sensitive adhesive layer in the masking film, heat-resistant adhesive film or masking heat-resistant adhesive film is usually 5 to 300 ⁇ m, preferably 5 to 50 ⁇ m, particularly preferably 10 to 30 ⁇ m. If this pressure-sensitive adhesive layer is too thin, the physical properties of the adhesive tend to be difficult to stabilize, and if it is too thick, the entire pressure-sensitive adhesive film tends to be too thick and the usability tends to deteriorate.
- the glass transition temperature (Tg) derived from the loss elastic modulus at 1 Hz of the pressure-sensitive adhesive layer of the masking film, heat-resistant adhesive film or masking heat-resistant adhesive film is usually 0 ° C. or lower, preferably ⁇ 30 ° C. or lower, particularly preferably ⁇ 45 ° C. It is as follows. If the Tg derived from the loss elastic modulus is too high, the pressure-sensitive adhesive becomes hard and the adhesive strength after heating tends to increase, and if it is too low, the heat-resistant stain resistance tends to deteriorate. Usually, the lower limit value of Tg derived from the loss modulus is ⁇ 56 ° C.
- the glass transition temperature (Tg) derived from the loss tangent (tan ⁇ ) at 1 Hz of the pressure-sensitive adhesive layer of the masking film, heat-resistant adhesive film or masking heat-resistant adhesive film is usually 0 ° C. or lower, preferably ⁇ 15 ° C. or lower, particularly preferably ⁇ It is 27 degrees C or less. If the Tg derived from tan ⁇ is too high, the pressure-sensitive adhesive becomes hard and the adhesive strength after heating tends to increase, and if it is too low, the heat-resistant stain resistance tends to deteriorate. Usually, the lower limit of Tg derived from loss tangent is ⁇ 40 ° C.
- the adhesive strength of the pressure-sensitive adhesive layer of the masking film, heat-resistant adhesive film or masking heat-resistant adhesive film is appropriately adjusted according to the material of the adherend, for example, SUS-BA plate, hard-coated PET film, When pasting on glass or the like, the initial adhesive strength is preferably 0.01 to 1.0 N / 25 mm, particularly preferably 0.05 to 0.8 N / 25 mm, and further preferably 0.1 to 0.00. 5 N / 25 mm.
- the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer is preferably 0.01 to 1.0 N / 25 mm after heat resistance, particularly preferably 0.05 to 0.9 N / 25 mm, more preferably 0.00. 1 to 0.8 N / 25 mm.
- the heat-resistant adhesive film for masking according to the present invention is used as a temporary heat-protective adhesive film for protecting a surface of a circuit board such as an FPC board or an ITO transparent electrode layer temporarily, or temporarily during a manufacturing process. It can be used as a heat-resistant pressure-sensitive adhesive film for temporary fixing for holding and reinforcing.
- Examples of the adherend to which the heat-resistant adhesive film for masking is to be attached include base materials made of the following materials.
- Metal plates or metal foils such as aluminum, copper, iron, stainless steel, magnesium, nickel, titanium; Polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer, ester acrylate; Polyethylene, chlorinated polyethylene, chlorosulfonated polyethylene, ethylene propylene rubber, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid Polyolefin resins such as acid copolymers, ionomers, polypropylene, polyallomer polybutylene, polymethylpentene; Polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetraflu
- heat-resistant materials include aluminum, copper, iron, stainless steel, magnesium, nickel, titanium and other metal plates or metal foils; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer Polyester resins such as ester acrylates; polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymers; polyimides and derivatives thereof; bisphenol-type epoxy resins, Examples include epoxy resin composite materials, alicyclic epoxy resins, epoxy novolacs, biphenyl type epoxy resins, and epoxy resins such as epoxy acrylate.
- the heat-resistant pressure-sensitive adhesive film for masking obtained using the pressure-sensitive adhesive composition of the present invention includes a carrier film for a process such as a printed circuit board, particularly a flexible printed circuit board; Protective film for printed circuit boards; protective film for solder plating of printed circuit boards; insulating and heat-resistant protective film for heat-resistant transformers; masking film during solder reflow process for electronic circuit boards; various temporary fixing and protective films for parts; Films for sealing, such as surface protective films for touch panel-related members such as ITO transparent electrode layers, and the like, and can be widely used in general masking applications requiring heat resistance and temporary fixing applications.
- a heat-resistant adhesive film for masking produced using the adhesive composition of the present invention is preferred.
- the masking heat-resistant adhesive film of the present invention is attached to the adherend surface, usually 100 ° C. or higher, preferably 120 ° C. or higher, particularly preferably 150 ° C. or higher, more preferably 170 ° C. After the above heating step, the masking heat-resistant adhesive film may be peeled off from the adherend surface.
- the heat-resistant adhesive film for masking of the present invention is resistant to contamination such as adhesive residue on the adherend when it is peeled off from the adherend after use under high temperature conditions. Is reduced. Moreover, since the heat-resistant adhesive film for masking of the present invention can be peeled off with a small force at the time of peeling after being used under high temperature conditions, the surface of the adherend can be prevented from being damaged, such as an ITO transparent electrode layer, etc. Damage to the thin film can be prevented. Furthermore, since the heat-resistant adhesive film for masking of the present invention is unlikely to cause corrosion on the metal adherend, the possibility of causing defects in the final product is also reduced.
- ethoxydiethylene glycol acrylate manufactured by Kyoeisha Chemical Co., Ltd., trade name “Light acrylate EC-A”, number of EO repeating units 2) (a1) 20 parts, butyl acrylate (BA) (a2) 73 8 parts, 1 part of methyl methacrylate (MMA) (a2), 5 parts of 2-hydroxyethyl methacrylate (HEMA) (a3), 0.2 part of dimethylaminopropylacrylamide (DMAPAA) (a4) and azobisisobutyronitrile A mixture in which 0.026 parts of (AIBN) was mixed and dissolved was dropped over 2 hours.
- BA butyl acrylate
- HEMA 2-hydroxyethyl methacrylate
- DMAPAA dimethylaminopropylacrylamide
- AIBN dimethylaminopropylacrylamide
- the polymerization catalyst solution in which 0.060 part of AIBN was dissolved in 2 parts of ethyl acetate was added successively and polymerized at the above temperature for 7 hours under reflux, and then diluted with ethyl acetate to obtain an acrylic resin ( A 35% solution of A-1) was obtained.
- ECA ethoxydiethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name “Light acrylate EC-A”, 2 EO repeat units)
- 2MTG Methoxytriethylene glycol acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat MTG”, number of EO repeating units 3)
- AME400 Methoxypolyethylene glycol acrylate (manufactured by NOF Corporation, trade name “Blemmer AME400”, number of EO repeating units 9)
- 2MEA Methoxyethylene glycol acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “2-MTA”, EO chain repeating unit number 1)
- -BA butyl acrylate-2EHA: 2-ethylhexyl acrylate-MMA: methyl methacrylate-HEMA: 2-hydroxyethyl methacrylate-AAc: acrylic acid
- the pressure-sensitive adhesive composition prepared above was applied to a polyimide film (thickness 25 ⁇ m) as a substrate so that the thickness after drying was about 25 ⁇ m, and then dried at 100 ° C. for 2 minutes. Thereafter, the coated surface was adhered to the coated surface to protect the coated surface, and cured for 7 days in an atmosphere at a temperature of 40 ° C. to obtain an adhesive film.
- the following evaluation was performed using the obtained adhesive film, and the results are summarized in Table 2.
- Adhesive strength after heating
- the above adhesive film of 25 mm x 100 mm was applied to a stainless steel plate (SUS304BA plate) as an adherend by applying 2 kg rubber roller in two reciprocations in an atmosphere of 23 ° C and relative humidity of 50%, and left in the same atmosphere for 30 minutes. After that, it was left to stand at 200 ° C. for 1 hour and returned to 23 ° C. Further, after being left for 2 hours in an atmosphere of 23 ° C. and 50% relative humidity, 180 ° peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min, and evaluated according to the following criteria.
- the adhesive films of Examples 1 to 12 not only the adhesive force immediately after application but also the adhesive force does not become excessive even after being used at a high temperature of 200 ° C. for 1 hour. It can be peeled off, and it can be seen that contamination hardly occurs when peeled off from the adherend.
- the copolymer component constituting the acrylic resin (A) the polyoxyethylene structure-containing monomer (a1) defined in the present invention is not contained or the content thereof is small. 6 and 8, it can be seen that, although the adhesive force immediately after application is not excessive, the adhesive force becomes excessive after use under high temperature conditions, and it is difficult to peel from the adherend with a small force.
- Comparative Example 7 in which the content of the polyoxyethylene structure-containing monomer (a1) specified in the present invention is too large, the adhesive strength does not become excessive even after use under high temperature conditions, but it peels off from the adherend. In this case, the contamination is clearly confirmed, and it is understood that the adherend contamination is large.
- the pressure-sensitive adhesive composition of the present invention is preferably used for a heat-resistant pressure-sensitive adhesive film for masking for masking and fixing in a heating process included in a manufacturing process of touch panel-related members such as circuit boards such as FPC boards and ITO transparent electrodes. Can do.
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Abstract
Description
これらの問題を解決するために、次のような技術が開示されている。
また、本発明は、この粘着剤組成物を架橋させてなる粘着剤、該粘着剤からなるマスキングフィルム用粘着剤、該粘着剤からなる耐熱粘着フィルム用粘着剤、該粘着剤からなる粘着剤層をフィルム上に有するマスキング用耐熱粘着フィルム、および該マスキング用耐熱粘着フィルムの使用方法の提供をも目的とするものである。
例えば、アクリル系樹脂の構成モノマーとして、ポリオキシエチレン構造を含有するモノマー成分を特定量含有する共重合成分を共重合してなるアクリル系樹脂を耐熱粘着フィルム用の粘着剤組成物として用いることにより、上記課題を解決できることを見出し、本発明の完成に到達した。
また、本発明の要旨は、ポリオキシエチレン構造含有モノマー(a1)、及び(メタ)アクリル酸アルキルエステル系モノマー(a2)を含有してなる共重合成分を共重合してなるアクリル系樹脂(A)を含有する粘着剤組成物であって、共重合成分中におけるポリオキシエチレン構造含有モノマー(a1)の含有量が、10~45重量%であることを特徴とする粘着剤組成物に関するものである。
なお、本発明における「粘着フィルム」とは、粘着シート、粘着フィルム、粘着テープを概念的に包含するものである。
ポリオキシエチレン構造含有モノマー(a1)のオキシエチレン鎖の繰り返し単位数は、通常、2個以上、好ましくは2~20個、特に好ましくは2~15個、更に好ましくは2~10個である。かかる繰り返し単位数が小さすぎると被着体へのなじみ性が悪くなる傾向があり、大きすぎると加熱後の被着体汚染が増大する傾向がある。
これらは1種を単独で又は2種以上を併せて用いることができる。
なお、アクリル系樹脂(A)におけるポリオキシエチレン構造含有モノマー(a1)由来の構造単位の含有量は、1H-NMRで測定して算出することができる。
例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、iso-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-オクチル(メタ)アクリレート、iso-オクチルアクリレート、イソデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、セチル(メタ)アクリレート、ステアリル(メタ)アクリレート、iso-ステアリル(メタ)アクリレート等の脂肪族の(メタ)アクリル酸アルキルエステル;シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート等の脂環族の(メタ)アクリル酸エステル等が挙げられる。
好ましい(メタ)アクリル酸アルキルエステル系モノマー(a2)としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、iso-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、n-ヘキシル(メタ)アクリレートが挙げられる。
これらは1種を単独で又は2種以上を併せて用いることができる。
なお、アクリル系樹脂(A)における(メタ)アクリル酸アルキルエステル系モノマー(a2)由来の構造単位の含有量は、1H-NMRで測定して算出することができる。
また、(メタ)アクリル酸アルキルエステル系モノマー(a2)中、炭素数が1~6のアルキル基を有する(メタ)アクリル酸アルキルエステル系モノマー(a2-1)の含有量が80重量%以上であることが加熱工程後の被着体汚染に優れる点で好ましく、特に好ましくは85重量%以上、更に好ましくは90重量%以上、殊に好ましくは95重量%以上である。
2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、3-クロロ2-ヒドロキシプロピル(メタ)アクリレート等の2級水酸基含有モノマー;
2,2-ジメチル2-ヒドロキシエチル(メタ)アクリレート等の3級水酸基含有モノマーを挙げることができる。
上記水酸基含有モノマーの中でも、架橋剤との反応性に優れる点で、2-ヒドロキシエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートを使用することが特に好ましい。
これらの中でも、効率的に架橋反応ができる点で、水酸基含有モノマーおよび/またはカルボキシル基含有モノマーが好ましく用いられる。これら官能基含有モノマー(a3)は、単独で用いてもよいし2種以上を併用してもよい。
なお、アクリル系樹脂(A)における官能基含有モノマー(a3)由来の構造単位の含有量は、1H-NMRで測定して算出することができる。
アミノエチル(メタ)アクリレート、N,N-ジメチルアミノメチル(メタ)アクリレート、N,N-ジメチルアミノエチル(メタ)アクリレート、t-ブチルアミノエチル(メタ)アクリレート等のアミノアルキル(メタ)アクリレート系モノマー;
フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、フェニルジエチレングリコール(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、スチレン、α―メチルスチレン等の1つの芳香環を含有するモノマー;
ビフェニルオキシエチル(メタ)アクリレート等のビフェニルオキシ構造含有(メタ)アクリル酸エステル系モノマー;
2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、メトキシジエチレングリコール(メタ)アクリレート、エトキシジエチレングリコール(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等のアルコキシ基またはオキシアルキレン基を含有するモノマー;
アクリロニトリル、メタクリロニトリル、酢酸ビニル、プロピオン酸ビニル、ステアリン酸ビニル、塩化ビニル、塩化ビニリデン、アルキルビニルエーテル、ビニルトルエン、ビニルピリジン、ビニルピロリドン、イタコン酸ジアルキルエステル、フマル酸ジアルキルエステル、アリルアルコール、アクリルクロライド、メチルビニルケトン、アリルトリメチルアンモニウムクロライド、ジメチルアリルビニルケトン等が挙げられる。これらの共重合性モノマーのうち、加熱工程後の被着体汚染を減少させる点で(メタ)アクリルアミド系モノマーが好ましい。
これらは1種を単独で又は2種以上を併せて用いることができる。
なお、アクリル系樹脂(A)におけるその他の共重合性モノマー(a4)由来の構造単位の含有量は、1H-NMRで測定して算出することができる。
また測定に際してポリマーを誘導体化してもよいし溶離液の種類を適宜変更してもよい。
Tga:モノマーaのホモポリマーのガラス転移温度(K)
Wa:モノマーaの重量分率
Tgb:モノマーbのホモポリマーのガラス転移温度(K)
Wb:モノマーbの重量分率
Tgn:モノマーnのホモポリマーのガラス転移温度(K)
Wn:モノマーnの重量分率(Wa+Wb+・・・+Wn=1)
これらの中でも耐熱性の点でヘキサメチレンジイソシアネートのイソシアヌレート体や2,4-トリレンジイソシアネートおよび/または2,6-トリレンジイソシアネートとトリメチロールプロパンとのアダクト体、2,4-トリレンジイソシアネートおよび/または2,6-トリレンジイソシアネートのイソシアヌレート体、テトラメチルキシリレンジイソシアネートとトリメチロールプロパンとのアダクト体が好ましい。
本発明において「帯電防止剤を含有しない」とは、通常、帯電防止剤を全く含有しないものであるが、粘着剤組成物が帯電防止性能を持たない程度に含有する場合があってもよく、具体的には、粘着剤組成物中、帯電防止剤の含有量が好ましくは0.1重量%以下、特に好ましくは0.05重量%以下、更に好ましくは0.01重量%以下であってもよい。
かかる帯電防止剤としては、例えば、イミダゾリウム塩、テトラアルキルアンモニウムスルホン酸塩等の第4級アンモニウム塩のカチオン型帯電防止剤;脂肪族スルホン酸塩、高級アルコール硫酸エステル塩、高級アルコールアルキレンオキサイド付加物硫酸エステル塩、高級アルコールリン酸エステル塩、高級アルコールアルコールアルキレンオキサイド付加物リン酸エステル塩等のアニオン型帯電防止剤;カリウムビス(フルオロスルホニル)イミド、リチウムビス(トリフルオロスルホニル)イミドや塩化リチウム等のアルカリ金属塩、アルカリ土類金属塩、高級アルコールアルキレンオキサイド付加物、ポリアルキレングリコール脂肪酸エステル等が挙げられる。
ゲル分率が低すぎると粘着剤の凝集力が低下し、糊残りを生じて、被着体汚染の原因となる傾向がある。
上記エージング処理は、粘着物性のバランスをとるために行なうものであり、エージングの条件としては、温度は通常、0~150℃、好ましくは10~100℃、特に好ましくは20~80℃、時間は通常、30日以下、好ましくは14日以下、特に好ましくは7日以下であり、具体的には、例えば23℃で3~10日間、40℃で1~7日間等の条件で行なうことができる。
マスキング用耐熱粘着フィルムの被着対象である被着体としては、下記に示す材料の基材が例示される。
ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリエチレンテレフタレート/イソフタレート共重合体、エステルアクリレート等のポリエステル系樹脂;
ポリエチレン、塩素化ポリエチレン、クロルスルフォン化ポリエチレン、エチレンプロピレンゴム、エチレン-酢酸ビニル共重合体、エチレン-エチルアクリレート共重合体、エチレン-イソブチルアクリレート共重合体、エチレン-アクリル酸共重合体、エチレン-メタクリル酸共重合体、アイノノマー、ポリプロピレン、ポリアロマーポリブチレン、ポリメチルペンテン等のポリオレフィン系樹脂;
ポリフッ化ビニル、ポリフッ化ビニリデン、ポリ4フッ化エチレン、エチレン-4フッ化エチレン共重合体等のポリフッ化エチレン系樹脂;
ポリスチレン、ポリαメチルスチレン、アクリロニトリル-スチレン共重合体、アクリロニトリル-ブタジエン-スチレン共重合体、アクリロニトリル-スチレン-アクリレート共重合体;
ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリアクリル酸エチル、ポリアクリル酸ブチル等のポリアルキル(メタ)アクリレートやメチルメタクリレート-スチレン共重合体、メチルメタクリレート-α-メチルスチレン共重合体等のアクリル系樹脂;
ポリ塩化ビニル、可塑化ポリ塩化ビニル、ABS変性ポリ塩化ビニル、後塩素化ポリ塩化ビニル、ポリ塩化ビニル-アクリル樹脂アロイ、塩化ビニル-プロピレン共重合体、塩化ビニル-酢酸ビニル共重合体、ポリ塩化ビニリデン等のポリ塩化ビニル重合体およびその誘導体;
ポリ酢酸ビニル、ポリビニルアルコール、ポリビニルフォルマール、ポリビニルブチラール、エチレン-ビニルアルコール共重合体、エチレン-酢酸ビニル共重合体、ビニロン等のポリ酢酸ビニル、およびその誘導体;
ポリビニルメチルエーテル、ポリビニルメチルケトン;
ポリホルムアルデヒド、アセタールコポリマー、ポリエチレンオキサイド、ポリプロピレンオキサイド、塩素化ポリエーテル、フェノキシ樹脂、ポリフェニレンオキサオド等のポリエーテル;
ポリテロラフルオロエチレン、ポリクロロトリフルオロエチレン、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、ポリフッ化ビニリデン、クロロトリフルオロエチレン-フッ化ビニリデン共重合体等のフッ化樹脂;
ポリカーボネート、ポリカーボネートABSアロイ;
ナイロン、ナイロン-6、ナイロン-6,6、ナイロン-6/6,6共重合体、ナイロン-6,10、ナイロン-6,12、ナイロン-11、ナイロン-12等のナイロン(ポリアミド)類;
ブタジエン-スチレン共重合体、ブタジエン系プラスチック;
ポリイミドおよびその誘導体、ポリスルホン、ポリフェニレンサルファイド、高アクリルニトリル共重合体;
けい素樹脂、半無機および無機高分子;
フェノール樹脂、フェノール-フルフラール樹脂、変性フェノール樹脂等のフェノール樹脂およびその誘導体;
フラン樹脂、キシレン樹脂、アニリン樹脂、アセトンホルムアルデヒド樹脂等のホルマリン樹脂;
不飽和ポリエステルとアルキッド樹脂;
ビスフェノール型エポキシ樹脂、エポキシ樹脂複合材料、脂環エポキシ樹脂、エポキシノボラック、ビフェニル型エポキシ樹脂、エポキシアクリレート等のエポキシ樹脂;
ポリウレタン、発泡ウレタン、ウレタンアクリレート等のポリウレタン;
ジアリルフタレート樹脂、トリアリルシアヌレート樹脂、ポリアリルスルホン、アリルジグリコールカーボネート、ポリアリルエーテル、ポリアリレート等のアリル樹脂;
セルロース系プラスチック、セルロースアセテート、セルロースプロピオネート、セルロースアセテートブチレート、エチルセルロース、ニトロセルロースとセルロイド等のセルロース系樹脂。
〔製造例1:アクリル系樹脂(A-1)〕
温度計、攪拌機、滴下ロート及び還流冷却器を備えた反応器内に、酢酸エチル119部、アセトン34.8部とアゾビスイソブチロニトリル(AIBN)0.01部を仕込み、撹拌しながら昇温し、70℃になったら、エトキシジエチレングリコールアクリレート(共栄社化学社製、商品名「ライトアクリレートEC-A」、EO繰り返し単位数2個)(a1)20部、ブチルアクリレート(BA)(a2)73.8部、メチルメタクリレート(MMA)(a2)1部、2-ヒドロキシエチルメタクリレート(HEMA)(a3)5部、ジメチルアミノプロピルアクリルアミド(DMAPAA)(a4)0.2部とアゾビスイソブチロニトリル(AIBN)0.026部を混合溶解させた混合物を2時間にわたって滴下した。更に、重合途中に、酢酸エチル2部にAIBN0.060部を溶解させた重合触媒液を逐次追加しながら前記温度で還流下7時間重合させた後、酢酸エチルで希釈して、アクリル系樹脂(A-1)の35%溶液を得た。
表1に示す配合にて製造例1と同様にしてアクリル系樹脂(A-2)~(A-12)、(A’-1)~(A’-8)の溶液を調製した。
・2MTG:メトキシトリエチレングリコールアクリレート(大阪有機化学工業社製、商品名「ビスコートMTG」、EO繰り返し単位数3個)
・AME400:メトキシポリエチレングリコールアクリレート(日油社製、商品名「ブレンマーAME400」、EO繰り返し単位数9個)
・2MEA:メトキシエチレングリコールアクリレート(大阪有機化学製、商品名「2-MTA」、EO鎖繰り返し単位数1個)
・BA:ブチルアクリレート
・2EHA:2-エチルヘキシルアクリレート
・MMA:メチルメタクリレート
・HEMA:2-ヒドロキシエチルメタクリレート
・AAc:アクリル酸
・DMAPAA:ジメチルアミノプロピルアクリルアミド
・BMAA:N-(n-ブトキシメチル)アクリルアミド(笠野興産社製、商品名「アマイドNBM-2」
〔粘着剤組成物の調製〕
製造例1~11、製造例13~19で得られたアクリル系樹脂(A-1)~(A-11)、(A’-1)~(A’-7)の固形分100部に対して、架橋剤(B-1)(東ソー株式会社製のイソシアネート系架橋剤、「コロネートHX」)を表2に記載のとおりに配合し、粘着剤組成物を調製した。
また、製造例12、20で得られたアクリル系樹脂(A-12)、(A’-8)の固形分100部に対して、架橋剤(B-2)(三菱ガス化学社製のエポキシ系架橋剤、「テトラッドC」)を表2に記載のとおりに配合し、粘着剤組成物を調製した。
上記で調製した粘着剤組成物を乾燥後の厚さが約25μmになるように、基材としてのポリイミドフィルム(厚さ25μm)に塗布した後、100℃で2分間乾燥させた。その後、塗工面に、離型処理されたPETを貼着して塗工面を保護し、温度40℃の雰囲気下で7日間養生し、粘着フィルムを得た。
得られた粘着フィルムを用いて下記の評価を行い、その結果を表2にまとめた。
被着体としてステンレス板(SUS304BA板)に、25mm×100mmの上記粘着フィルムを23℃、相対湿度50%の雰囲気下にて2kgゴムローラー2往復で加圧貼付し、同雰囲気下で30分放置した後、剥離速度300mm/minで180度剥離強度(N/25mm)を測定し、以下の基準で評価した。
○:0.5N/25mm未満
△:0.5N/25mm以上、1.0N/25mm未満
×:1.0N/25mm以上
被着体としてステンレス板(SUS304BA板)に、25mm×100mmの上記粘着フィルムを23℃、相対湿度50%の雰囲気下にて2kgゴムローラー2往復で加圧貼付し、同雰囲気下で30分放置した後、200℃条件下で1時間放置し23℃に戻した。さらに23℃、相対湿度50%の雰囲気下にて2時間放置した後、剥離速度300mm/minで180度剥離強度(N/25mm)を測定し、以下の基準で評価した。
○:0.8N/25mm未満
△:0.8N/25mm以上、1.0N/25mm未満
×:1.0N/25mm以上
得られた耐熱粘着フィルムを用いて25mm×100mmの大きさの試験片を作製し(切り出し)、この試験片を被着体(SUS304BA板)に2kgローラーを2往復させる方法で圧着し、表2に記載の温度と時間で放置し23℃に戻した。さらに23℃、相対湿度50%雰囲気下で2時間放置した後、剥離速度300mm/minで180度剥離した後の被着体表面の様子を観察し、以下の基準で評価した。
◎:全く汚染が確認されなかった。
○:汚染がほとんど確認されなかった。
△:僅かに汚染が確認された。
×:明らかに汚染が確認された。
次に、上記で得られた粘着剤組成物を、乾燥後の厚さが約150μmになるように、離型処理されたPET基材に塗布した後、常温で5分間乾燥させ、その後80℃で5分間乾燥させた。その後、塗工面に、離型処理されたPETを貼着して塗工面を保護し、温度40℃の雰囲気下で7日間養生し、粘弾性測定用の粘着フィルムを得た。
得られた粘弾性測定用の粘着フィルムを用いて下記の評価を行い、その結果を表2にまとめた。
粘弾性測定装置(アイティー計測制御社製 DVA-255)を用いて、測定周波数1Hzで、-100~200℃まで昇温速度3℃/minで、粘弾性測定用の粘着フィルムを昇温しながら、連続的に損失弾性率を測定した。損失弾性率が最も高くなる温度を、損失弾性率由来のガラス転移温度とした。また、損失正接(tanδ)が最も高くなる温度を、損失正接(tanδ)由来のガラス転移温度とした。
一方、アクリル系樹脂(A)を構成する共重合成分中に、本発明で規定するポリオキシエチレン構造含有モノマー(a1)が含有されていなかったり、あるいはその含有量が少なかったりする比較例1~6、8では、貼付直後の粘着力は過大ではないものの、高温条件下で使用した後において粘着力が過大となり、小さな力で被着体から剥離するのが困難であることが分かる。また、本発明で規定するポリオキシエチレン構造含有モノマー(a1)の含有量が多すぎる比較例7では、高温条件下での使用後においても粘着力が過大にはならないものの、被着体から剥離した際に明らかに汚染が確認され、被着体汚染が大きいことが分かる。
Claims (13)
- ポリオキシエチレン構造含有モノマー(a1)由来の構造単位、および
(メタ)アクリル酸アルキルエステル系モノマー(a2)由来の構造単位を有するアクリル系樹脂(A)を含有する粘着剤組成物であって、
ポリオキシエチレン構造含有モノマー(a1)由来の構造単位の含有量が、10~45重量%であり、
帯電防止剤を含有しないことを特徴とする粘着剤組成物。 - ポリオキシエチレン構造含有モノマー(a1)、および
(メタ)アクリル酸アルキルエステル系モノマー(a2)を含有してなる共重合成分を共重合してなるアクリル系樹脂(A)を含有する粘着剤組成物であって、
共重合成分中におけるポリオキシエチレン構造含有モノマー(a1)の含有量が、10~45重量%であり、
帯電防止剤を含有しないことを特徴とする粘着剤組成物。 - ポリオキシエチレン構造含有モノマー(a1)が、ポリオキシエチレン構造含有(メタ)アクリレート系モノマーであることを特徴とする請求項1または2に記載の粘着剤組成物。
- ポリオキシエチレン構造含有モノマー(a1)のオキシエチレン鎖の繰り返し単位数が2~20個であることを特徴とする請求項1~3のいずれか一項に記載の粘着剤組成物。
- 共重合成分が水酸基含有モノマーおよび/またはカルボキシル基含有モノマーを含有することを特徴とする請求項2~4のいずれか一項に記載の粘着剤組成物。
- 共重合成分が(メタ)アクリルアミド系モノマーを含有することを特徴とする請求項2~5のいずれか一項に記載の粘着剤組成物。
- アクリル系樹脂(A)の重量平均分子量が10万~250万であることを特徴とする請求項1~6のいずれか一項に記載の粘着剤組成物。
- 架橋剤(B)を更に含有することを特徴とする請求項1~7のいずれか一項に記載の粘着剤組成物。
- 請求項8に記載の粘着剤組成物が架橋されてなることを特徴とする粘着剤。
- 請求項9に記載の粘着剤からなることを特徴とするマスキングフィルム用粘着剤。
- 請求項9に記載の粘着剤からなることを特徴とする耐熱粘着フィルム用粘着剤。
- 請求項9に記載の粘着剤からなる粘着剤層をフィルム上に有することを特徴とするマスキング用耐熱粘着フィルム。
- 請求項12に記載のマスキング用耐熱粘着フィルムを被着体表面に貼り付け、100℃以上の加熱工程に付した後、そのマスキング用耐熱粘着フィルムを被着体表面から剥離することを特徴とするマスキング用耐熱粘着フィルムの使用方法。
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JP2018131493A (ja) * | 2017-02-14 | 2018-08-23 | 東洋インキScホールディングス株式会社 | 表面保護用粘着剤および表面保護シート |
WO2018181550A1 (ja) * | 2017-03-29 | 2018-10-04 | 住化積水フィルム株式会社 | メッキ工程搬送用テープ基材及びメッキ工程搬送用テープ |
JPWO2017145545A1 (ja) * | 2016-02-25 | 2018-12-06 | 株式会社寺岡製作所 | 粘着剤組成物及び粘着テープ |
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JP2019167458A (ja) * | 2018-03-23 | 2019-10-03 | リンテック株式会社 | 粘着フィルム |
JP2020012042A (ja) * | 2018-07-17 | 2020-01-23 | リンテック株式会社 | マスキングシート |
WO2021075188A1 (ja) * | 2019-10-15 | 2021-04-22 | 綜研化学株式会社 | 粘着剤組成物および粘着シート |
JP2021063204A (ja) * | 2019-10-17 | 2021-04-22 | Dic株式会社 | 粘着剤組成物 |
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JPWO2017145545A1 (ja) * | 2016-02-25 | 2018-12-06 | 株式会社寺岡製作所 | 粘着剤組成物及び粘着テープ |
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JP2018203823A (ja) * | 2017-05-31 | 2018-12-27 | 日立化成株式会社 | 表面保護フィルム用粘着剤組成物、表面保護膜、及び表面保護フィルム |
JP7091610B2 (ja) | 2017-05-31 | 2022-06-28 | 昭和電工マテリアルズ株式会社 | 表面保護膜、及び表面保護フィルム |
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JP2020012042A (ja) * | 2018-07-17 | 2020-01-23 | リンテック株式会社 | マスキングシート |
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WO2021075188A1 (ja) * | 2019-10-15 | 2021-04-22 | 綜研化学株式会社 | 粘着剤組成物および粘着シート |
JP2021063204A (ja) * | 2019-10-17 | 2021-04-22 | Dic株式会社 | 粘着剤組成物 |
JP7375451B2 (ja) | 2019-10-17 | 2023-11-08 | Dic株式会社 | 粘着剤組成物 |
Also Published As
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TWI668284B (zh) | 2019-08-11 |
TW201612277A (en) | 2016-04-01 |
JP6996834B2 (ja) | 2022-01-17 |
JPWO2016027787A1 (ja) | 2017-06-01 |
KR20170043619A (ko) | 2017-04-21 |
CN106574161B (zh) | 2019-06-14 |
CN106574161A (zh) | 2017-04-19 |
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