Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • 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
  • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
  • C09J125/02—Homopolymers or copolymers of hydrocarbons
  • C09J125/04—Homopolymers or copolymers of styrene
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

• the present invention relates to an adhesive composition and an adhesive tape provided with an adhesive layer comprising the adhesive composition.
• the adhesive strength of the adhesive tape generally decreases as the thickness of the adhesive layer decreases.
• the adhesive force is significantly reduced. For this reason, it is difficult to develop a sufficiently strong adhesive force even under thin film conditions, and there is a strong demand for the development of an adhesive tape having a high adhesive force even when thin.
• Patent Document 1 discloses a pressure-sensitive adhesive composition for a thin film in which a tackifier resin is added in an amount of 40% by mass to 60% by mass based on the pressure-sensitive adhesive, and forms a pressure-sensitive adhesive layer of 2 to 10 ⁇ m.
• the tackifying resin used in the example of Patent Document 1 is a rosin-based resin.
• the rosin-based resin is yellow to orange, and the color of the sheet may be a problem.
• the compatibility with the acrylic pressure-sensitive adhesive is poor, the adhesive strength cannot be greatly improved, and the haze may become a problem.
• rosin-based resins have a carboxyl group or a hydroxyl group in the structure, and may hinder cross-linking between pressure-sensitive adhesives. For this reason, when a large amount of the rosin-based resin is used, the holding power and the constant load releasability may deteriorate.
• Patent Document 2 discloses a pressure-sensitive adhesive composition containing a (meth) acryl-based polymer derived from n-butyl acrylate, a tackifier resin, and a cross-linking agent. Since the average molecular weight is 500,000, the adhesive strength is not high, and since the tackifier resin used is a rosin-based resin, it is presumed that the color is not preferable.
• an object of the present invention is to provide a pressure-sensitive adhesive composition having high adhesive strength and exhibiting high adhesiveness even when the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape used is thin.
• (Meth) acrylic polymer (A) is a polymer obtained by polymerizing a monomer containing 60% by mass or more of n-butyl (meth) acrylate (a1)
• the content of the synthetic hydrocarbon-based tackifying resin (B) is 40% by mass or more and 60% by mass or less based on the total mass of the (meth) acrylic polymer (A) and the synthetic hydrocarbon-based tackifying resin (B).
• a pressure-sensitive adhesive composition comprising: [2] The pressure-sensitive adhesive composition according to [1], wherein the synthetic hydrocarbon-based tackifying resin (B) is a styrene-based resin. [3] The pressure-sensitive adhesive composition according to [1] or [2], further comprising a crosslinking agent. [4]
• the (meth) acrylic polymer (A) is a polymer obtained by polymerizing a monomer containing a (meth) acrylic monomer containing 80% by mass or more of n-butyl (meth) acrylate, [1] to [1].
• the pressure-sensitive adhesive composition according to any one of 3).
• the pressure-sensitive adhesive composition of the present invention can provide a pressure-sensitive adhesive tape having high tackiness. Furthermore, even a thin adhesive tape shows high adhesiveness, so that it can be used for small OA equipment and electronic equipment.
• the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) having a weight average molecular weight of 700,000 or more and a synthetic hydrocarbon-based tackifying resin (B),
• (Meth) acrylic polymer (A) is a polymer obtained by polymerizing a monomer containing 60% by mass or more of n-butyl (meth) acrylate (a1), and (meth) acrylic polymer (A) and synthetic hydrocarbon
• the content of the synthetic hydrocarbon-based tackifying resin (B) is 40% by mass or more and 60% by mass or less with respect to the total mass of the system-based tackifying resin (B).
• the configuration will be specifically described.
• the pressure-sensitive adhesive composition of the present invention contains a (meth) acrylic polymer (A).
• the (meth) acrylic polymer (A) is obtained by polymerizing at least n-butyl (meth) acrylate (a1) and, if necessary, a monomer having a copolymerizability.
• the (meth) acrylate monomer is a monomer having a (meth) acryloyl group.
• Examples of the monomer component forming the (meth) acrylic polymer (A) include, in addition to n-butyl (meth) acrylate (a1), for example, a monomer (a2) and a monomer (a3) described below.
• (meth) acryl means both “acryl” and “methacryl”
• (meth) acrylate includes both “acrylate” and “methacrylate”.
• (Meth) acryloyl is meant to include both “acryloyl” and “methacryloyl”.
• n-butyl (meth) acrylate (a1) is 60% by mass or more, preferably 70% by mass, from the viewpoint of heat resistance and adhesiveness of the adhesive composition. %, More preferably 80% by mass or more.
• the monomer forming the (meth) acrylic polymer (A) may further include a monomer (a2).
• the monomer (a2) include alkyl (meth) acrylates other than n-butyl (meth) acrylate, alicyclic-containing (meth) acrylate, aryl (meth) acrylate, aralkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, and alkoxy.
• Examples include polyalkylene glycol mono (meth) acrylate and aryloxyalkyl (meth) acrylate.
• alkyl (meth) acrylate other than n-butyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and isobutyl (meth) acrylate Tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate,
• alicyclic-containing (meth) acrylate examples include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate.
• cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate.
• Aryl (meth) acrylate includes, for example, phenyl (meth) acrylate, and aralkyl (meth) acrylate includes, for example, benzyl (meth) acrylate.
• alkoxyalkyl (meth) acrylate examples include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, and 3-ethoxypropyl ( (Meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
• alkoxypolyalkylene glycol mono (meth) acrylate examples include methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, Methoxytriethylene glycol mono (meth) acrylate is exemplified.
• aryloxyalkyl (meth) acrylate examples include phenoxymethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-tolyloxyethyl (meth) acrylate, xylyloxymethyl (meth) acrylate, and naphthyloxymethyl (Meth) acrylates.
• the monomer (a2) may be used alone or in combination of two or more.
• the total amount of the n-butyl (meth) acrylate (a1) and the monomer (a2) is preferably 70% by mass or more, more preferably 80% by mass. And more preferably 85% by mass.
• the monomer forming the (meth) acrylic polymer (A) preferably contains the monomer (a3).
• the monomer (a3) is a crosslinkable group-containing monomer.
• Examples of the crosslinkable group-containing monomer include a carboxyl group-containing monomer and a hydroxyl group-containing monomer.
• carboxyl group-containing monomer examples include (meth) acrylic acid, ⁇ -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, crotonic acid, maleic acid, and fumaric acid.
• hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Hydroxy-3-phenoxypropyl (meth) acrylate;
• the monomer (a3) may be used alone or in combination of two or more.
• the amount of the monomer (a3) used is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and Preferably it is 1 to 8% by mass.
• an appropriate crosslinked structure can be formed by the reaction between the (meth) acrylic polymer (A) and a crosslinking agent described below.
• the monomer having copolymerizability may further include another monomer (a4) other than (a1) to (a3).
• Other monomers (a4) include, for example, amino group-containing monomers, amide group-containing monomers, glycidyl group-containing monomers, vinyl group-containing monomers, and polymerizable macromonomers.
• Amino group-containing monomers include, for example, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; amide group-containing monomers include, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N -Ethyl (meth) acrylamide; glycidyl group-containing monomers include, for example, glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether; vinyl group-containing monomers include, for example, vinyl acetate , Ethylene, propylene, isobutylene, vinyl chloride, styrene, ⁇ -methylstyrene, butadiene, isoprene and chloroprene.
• Examples of the polymerizable macromonomer include a macromonomer whose main chain constituent monomer is methyl methacrylate (product name: 45% AA-6 (AA-6S), AA-6; manufactured by Toagosei Co., Ltd.), a main chain constituent monomer Is a butyl acrylate (product name: AB-6; manufactured by Toagosei Co., Ltd.)
• a macromonomer whose main chain is a copolymer of styrene / acrylonitrile product name: AN-6S; manufactured by Toagosei Co., Ltd.
• the other monomer (a4) may be used alone or in combination of two or more.
• the amount of the other monomer (a4) used is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10 mass% or less.
• the weight average molecular weight (Mw) of the (meth) acrylic polymer (A) measured by the gel permeation chromatography (GPC) method is at least 700,000, preferably at least 800,000 from the viewpoint of adhesiveness. Preferably it is 900,000 or more.
• the molecular weight distribution (Mw / Mn) of the (meth) acrylic polymer (A) is preferably 20 or less, more preferably 1.5 to 18, and still more preferably 1.8 to 15.
• the glass transition temperature (Tg) of the (meth) acrylic polymer (A) is preferably lower than 0 ° C, more preferably -80 to -10 ° C, and still more preferably -70 to -20 ° C.
• the Tg of the (meth) acrylic polymer (A) can be determined by the Fox equation, and the Tg of the homopolymer formed from each monomer in the Fox equation is described in Polymer ⁇ Handbook ⁇ Fourth ⁇ Edition (Wiley-Interscience 2003). Values can be adopted.
• the (meth) acrylic polymer (A) can be produced by polymerizing or copolymerizing the above monomer component.
• the copolymer may be any of a random copolymer, a block copolymer and a graft copolymer, but a random copolymer is preferred.
• the (meth) acrylic polymer (A) can be produced, for example, by a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, and a suspension polymerization method. Among these, the solution polymerization method is preferable. .
• a monomer component, a polymerization initiator, and if necessary, other components such as a chain transfer agent and a polymerization solvent are charged into a reaction vessel, and the reaction initiation temperature is set at 40 to 100 ° C.
• the reaction is maintained at a temperature of 50 to 90 ° C. for 2 to 20 hours.
• the reaction is performed in an atmosphere of an inert gas such as nitrogen gas.
• at least one selected from a monomer component, a polymerization initiator, a chain transfer agent and a polymerization solvent may be additionally added.
• polymerization initiator examples include thermal polymerization initiators such as an azo-based initiator and a peroxide-based polymerization initiator.
• azo initiator examples include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2- Cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbo) Nitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′- Azobis (N, N'-dimethyleneisobutylamidine), 2,2'-azobis
• peroxide-based polymerization initiator examples include t-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propylperoxydicarbonate.
• the polymerization initiator may be used alone or in combination of two or more.
• the amount of the polymerization initiator to be used is usually 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass, based on 100 parts by mass of the total of the monomer components. It is.
• polymerization solvent examples include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; cyclopentane, cyclohexane, cycloheptane, and cyclohexane.
• Alicyclic hydrocarbons such as octane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, 1,2- Halogenated hydrocarbons such as dichloroethane and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and cyclohexanone.
• ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dio
• N N- dimethylformamide, N, N- dimethylacetamide, N- amides such as methylpyrrolidone; acetonitrile, nitriles such as benzonitrile; dimethylsulfoxide, sulfoxide and sulfolane.
• One type of polymerization solvent may be used alone, or two or more types may be used.
• the pressure-sensitive adhesive composition of the present invention contains a synthetic hydrocarbon-based tackifying resin (B).
• the synthetic hydrocarbon-based tackifying resin (B) is not particularly limited as long as it is a petroleum-based resin and a material that can impart tackiness to the pressure-sensitive adhesive composition.
• the molecular weight of the synthetic hydrocarbon-based tackifying resin (B) is preferably 800 or more, more preferably 1000 or more, and further preferably 1100 or more, from the viewpoint of heat resistance.
• the petroleum-based adhesive resin is a polymer, it represents a weight average molecular weight (Mw).
• the softening point of the synthetic hydrocarbon-based tackifying resin (B) is preferably 80 ° C or higher, more preferably 85 ° C or higher, further preferably 90 ° C or higher from the viewpoint of heat resistance.
• Examples of the synthetic hydrocarbon-based tackifying resin (B) include petroleum resins, styrene-based resins, and cumarone-indene resins. Among them, a styrene resin is preferable from the viewpoint of compatibility (appearance) with an acrylic polymer containing n-butyl (meth) acrylate as a main component.
• Petroleum resins include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, aliphatic / aromatic copolymer (C5 / C9) petroleum resins, and hydrogenated products thereof (for example, aromatics). Alicyclic petroleum resin obtained by hydrogenating an aromatic petroleum resin).
• the petroleum resin include, for example, Quinton A, B, R, CX series (all manufactured by Zeon Corporation), Alcon P-90, Alcon P-100, Alcon P-115, Alcon P-125, Alcon P-135, Archon M-90, Archon M-100, Archon M-115 (all manufactured by Arakawa Chemical Industries, Ltd.), Nisseki Neopolymer L-90, 120, 130, 140, 150, 170S, S, T -REZ HA085, HA103, HA105, HA125 (all manufactured by JXTG Energy Co., Ltd.).
• styrene-based tackifying resin examples include a styrene-based polymer, an ⁇ -methylstyrene-based polymer, a styrene- ( ⁇ -methylstyrene) -based copolymer, a styrene-aliphatic hydrocarbon-based copolymer, and styrene- ( ⁇ -Methylstyrene) -aliphatic hydrocarbon-based copolymer, styrene-aromatic hydrocarbon-based copolymer and the like.
• FMR-0150, FTR-0100, FTR-2120, FTR-2140, FTR-6100, FTR-6110, FTR-6125, FTR-7100, FTR-8100, FTR-8120 or more, Manufactured by Mitsui Chemicals, Inc.
• FMR-0150, FTR-0100, FTR-2120, FTR-2140, FTR-6100, FTR-6110, FTR-6125, FTR-7100, FTR-8100, FTR-8120 or more, Manufactured by Mitsui Chemicals, Inc.
• YS Resin SX-100 manufactured by Yashara Chemical Co., Ltd.
• coumarone-indene resin examples include, for example, Coumarone G-90, V-120, L-5 (all manufactured by Nikki Chemical Co., Ltd.).
• Synthetic hydrocarbon-based tackifying resin (B) may be used alone or in combination of two or more, but preferably contains at least one styrene-based resin.
• Tackifying resins other than the synthetic hydrocarbon-based tackifying resin (B) can be used as long as the properties are not impaired.
• the tackifying resin other than the synthetic hydrocarbon-based tackifying resin include a rosin-based tackifying resin, a terpene-based tackifying resin, and a terpene-phenol-based tackifying resin.
• the lower limit of the content of the synthetic hydrocarbon-based tackifying resin (B) is based on the total amount of the (meth) acrylic polymer (A) and the synthetic hydrocarbon-based tackifying resin (B). And at least 40% by mass.
• the upper limit of the content of the synthetic hydrocarbon-based tackifying resin (B) is 60% by mass or less based on the total amount of the (meth) acrylic polymer (A) and the synthetic hydrocarbon-based tackifying resin (B). And preferably 55% by mass or less.
• the composition of the pressure-sensitive adhesive composition may be adjusted so that the total of the tackifier resins falls within the above range.
• the crosslinking agent contained in the pressure-sensitive adhesive composition has reactivity with the crosslinking group of the (meth) acrylic polymer (A).
• crosslinking agent examples include an isocyanate compound, an epoxy compound, and a metal chelate compound.
• an isocyanate compound having two or more isocyanate groups in one molecule is usually used, preferably 2 to 8, more preferably 3 to 6.
• the number of isocyanate groups is in the above range, it is preferable in terms of the efficiency of the crosslinking reaction between the (meth) acrylic polymer (A) and the isocyanate compound, and in keeping the flexibility of the pressure-sensitive adhesive layer.
• Examples of the diisocyanate compound having two isocyanate groups in one molecule include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.
• aliphatic diisocyanate ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl
• Examples thereof include aliphatic diisocyanates having 4 to 30 carbon atoms such as -1,6-hexamethylene diisocyanate.
• alicyclic diisocyanate examples include C7-30 alicyclic diisocyanates such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethyl xylene diisocyanate. Diisocyanates.
• aromatic diisocyanate examples include an aromatic diisocyanate having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate.
• Examples of the isocyanate compound having three or more isocyanate groups in one molecule include an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate. Specific examples include 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatebenzene, and 4,4 ', 4 "-triphenylmethanetriisocyanate.
• Examples of the isocyanate compound include, for example, multimers (for example, dimer or trimer, biuret, isocyanurate) and derivatives (for example, polyhydric alcohols) of the above isocyanate compounds having two or more isocyanate groups.
• Examples of the polyhydric alcohol in the derivative include low-molecular-weight polyhydric alcohols such as trimethylolpropane, glycerin, and trihydric or higher alcohols such as pentaerythritol; and high-molecular-weight polyhydric alcohols such as polyether polyols.
• Examples include polyester polyol, acrylic polyol, polybutadiene polyol, and polyisoprene polyol.
• Such isocyanate compounds include, for example, trimer of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, biuret or isocyanurate of hexamethylene diisocyanate or tolylene diisocyanate, trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate.
• Reaction product e.g., triadduct of tolylene diisocyanate or xylylene diisocyanate
• reaction product of trimethylolpropane and hexamethylene diisocyanate e.g., adduct of hexamethylene diisocyanate
• polyether polyisocyanate e.g., adduct of hexamethylene diisocyanate
• Polyester polyisocyanate is exemplified.
• xylylene diisocyanate-based and hexamethylene diisocyanate-based cross-linking agents are preferable from the viewpoint of hard yellowing, and tolylene diisocyanate-based cross-linking agents are preferable from the viewpoint of stress relaxation.
• xylylene diisocyanate-based cross-linking agent include xylylene diisocyanate and its multimers, derivatives, and polymers.
• hexamethylene diisocyanate-based cross-linking agent include hexamethylene diisocyanate, its multimers, derivatives, and polymers.
• examples of the tolylene diisocyanate-based cross-linking agent include tolylene diisocyanate and its multimers, derivatives, and polymers.
• Examples of the epoxy compound include compounds having two or more epoxy groups in a molecule. Examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamineglycidylamine, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N'- Diamine glycidylaminomethyl).
• the metal chelate compound examples include, for example, aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, and other polyvalent metals, alkoxide, acetylacetone, ethyl acetoacetate, and the like coordinated.
• Compounds. Specific examples include aluminum isopropylate, aluminum secondary butyrate, aluminum ethyl acetoacetate diisopropylate, aluminum trisethyl acetoacetate, and aluminum trisacetylacetonate.
• the crosslinking agent may be used alone or in combination of two or more.
• the crosslinking agent is preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the total of the (meth) acrylic polymer (A) and the synthetic hydrocarbon-based tackifying resin (B). More preferably, the content is 0.05 to 3 parts by mass, and still more preferably 0.1 to 2.5 parts by mass. In such an embodiment, excellent adhesive properties can be realized.
• the pressure-sensitive adhesive composition of the present invention may contain various additives such as a silane coupling agent, an organopolysiloxane compound, a pigment, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler.
• the content of the additive is not particularly limited, but should be within a range that does not impair the properties of the double-sided pressure-sensitive adhesive sheet of the present invention and the pressure-sensitive adhesive composition used for the double-sided pressure-sensitive adhesive sheet.
• a silane coupling agent when added, it can be contained in an amount of more than 0% by mass and 3% by mass or less, preferably 2% by mass or less, more preferably 0.01 to 1% by mass, based on the whole pressure-sensitive adhesive composition. % Or less.
• a flame retardant may be contained, it is preferably less than 24 parts by mass with respect to 100 parts by mass in total of the (meth) acrylic polymer (A) and the synthetic hydrocarbon-based tackifying resin (B).
• the pressure-sensitive adhesive composition of the present invention may contain an organic solvent in order to adjust coatability.
• the organic solvent include the polymerization solvents described in the section of the production conditions for the (meth) acrylic polymer (A).
• the content of the organic solvent in the pressure-sensitive adhesive composition is usually 30 to 90% by mass, preferably 40 to 90% by mass.
• the pressure-sensitive adhesive tape of the present invention comprises a substrate and a pressure-sensitive adhesive layer formed on at least one of both surfaces of the substrate. Therefore, the pressure-sensitive adhesive tape of the present invention has a structure of at least two layers of a base material and a pressure-sensitive adhesive layer, and has a structure of at least three layers when forming a pressure-sensitive adhesive layer on both surfaces of the base material. I have. A release film may be attached to a surface of the pressure-sensitive adhesive layer that is not in contact with the substrate.
• the pressure-sensitive adhesive tape of the present invention includes a substrate.
• the thickness of the substrate used for the pressure-sensitive adhesive tape of the present invention is not particularly limited, but when the pressure-sensitive adhesive tape is reduced in thickness, the thickness is preferably 1 to 12 ⁇ m. If it is 1 ⁇ m or more, an appropriate sheet strength can be obtained, and if it is 12 ⁇ m or less, the increase in adhesion can be suppressed.
• the substrate is preferably thin. In that case, the thickness of the substrate is preferably 10 ⁇ m or less, particularly preferably 6 ⁇ m or less.
• polycarbonate PC
• PMMA polymethyl methacrylate
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• PEN polyethylene
• PE polypropylene
• Plastic films such as ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), polyamide (nylon), polyimide, and polyvinyl chloride (PVC) can be given.
• the substrate include glass, paper, and nonwoven fabric.
• the substrate is preferably a plastic film because it is smooth.
• the substrate is more preferably PET.
• a base material in which a black color material such as a black pigment or a white color material such as a white pigment is dispersed and contained may be used.
• the pressure-sensitive adhesive layer provided on at least one surface of the substrate can be formed from the pressure-sensitive adhesive composition of the present invention.
• the pressure-sensitive adhesive layers on both surfaces of the substrate may be the same or different.
• the thickness of the pressure-sensitive adhesive layer is not particularly limited, but when the pressure-sensitive adhesive tape is reduced in thickness, the thickness is preferably 1 to 12 ⁇ m. If it is 1 ⁇ m or more, an adhesive tape having an appropriate adhesive strength can be obtained, and if it is 12 ⁇ m or less, the increase in adhesion can be suppressed.
• the total thickness of the adhesive tape excluding the release film is preferably 25 ⁇ m or less, more preferably 15 ⁇ m or less, and still more preferably 10 ⁇ m or less. is there. Further, it is preferable that the pressure-sensitive adhesive layer occupies 40% or more of the total thickness of the pressure-sensitive adhesive tape excluding the release film. By doing so, a sufficient adhesive strength of the adhesive tape can be secured.
• the gel fraction of the pressure-sensitive adhesive layer is preferably from 10 to 98% by mass, more preferably from 20 to 90% by mass, and still more preferably from 30 to 85% by mass from the viewpoint of cohesive force, adhesive force to be described later, and proper re-sticking. %.
• the pressure-sensitive adhesive tape of the present invention can be used for various applications because it has a strong adhesive force while being a thin film as described above.
• a heat dissipation sheet or a light-shielding tape can be attached to a target article.
• the heat radiation sheet and the light shielding tape will be described.
• the heat dissipation sheet can be dissipated to the entire area of OA equipment and electronic equipment by installing it in a local high temperature part.
• the graphite sheet used for the heat radiation sheet include a natural graphite sheet obtained by forming natural graphite powder into a sheet, and an artificial graphite sheet obtained by heat-treating a polymer film.
• the polymer film for example, polyimide, polyamide, polyoxadiazole, polybenzothiazole, polybenzobisthiazole, polybenzoxazole, polybenzobisoxazole, polyparaphenylenevinylene, polybenzimidazole, polybenzobisimidazole, poly Films made of thiazole and the like are included.
• the thickness of the graphite sheet is preferably from 10 to 100 ⁇ m, more preferably from 15 to 50 ⁇ m. By setting the thickness of the graphite sheet within the above range, it is suitably used for fixing parts of OA equipment and electronic equipment.
• Light-shielding tape can prevent a problem caused by leaked light by using, for example, a non-self-luminous display unit such as a liquid crystal display module unit and a backlight unit.
• a non-self-luminous display unit such as a liquid crystal display module unit and a backlight unit.
• the pressure-sensitive adhesive tape of the present invention can be manufactured as follows. The case where pressure-sensitive adhesive layers are provided on both surfaces will be described as an example. One side of the release film is coated with the pressure-sensitive adhesive composition of the present invention so as to have a predetermined thickness after drying, and dried at 60 to 100 ° C. for 1 to 10 minutes to remove the solvent. Thereafter, the obtained pressure-sensitive adhesive layer is bonded to one surface of the base material (referred to as the first surface of the base material).
• the pressure-sensitive adhesive composition is applied to one surface of another release film so that the thickness after drying becomes a predetermined thickness. Then, the pressure-sensitive adhesive layer obtained by drying at 60 to 100 ° C. for 1 to 10 minutes and removing the solvent is used as the second side of the substrate (the second surface of the substrate). To produce a double-sided pressure-sensitive adhesive tape.
• the coating method is not particularly limited, and a conventionally known method can be used.
• Examples of the method for applying the pressure-sensitive adhesive composition include a method using a roll coater, a fountain coater, a lip coater, a knife coater, a die coater, a gravure coater, a reverse coater, a lip coater, a curtain coater, a slit die coater, and the like.
• the pressure-sensitive adhesive layer formed on the first surface and the pressure-sensitive adhesive layer formed on the second surface may be the same or different.
• Example 1 80 parts by mass of the synthetic hydrocarbon-based tackifying resin (B) (FTR-6100: manufactured by Mitsui Chemicals, Inc.) ((A) and (B) are based on 100 parts by mass of the solid content of the (meth) acrylic polymer (A-1). Ratio of (B) to the total of B): 44% by mass), an isocyanate crosslinking agent (L-45: manufactured by Soken Chemical Co., Ltd.) and a (meth) acrylic polymer (A-1) and a synthetic hydrocarbon-based tackifying resin ( 1.5 parts by mass (solid content) were mixed with respect to the total of B) to obtain PSA composition 1.
• FTR-6100 manufactured by Mitsui Chemicals, Inc.
• the pressure-sensitive adhesive composition 1 was applied on a release-treated polyethylene terephthalate (PET) release film so as to have a thickness of 2 ⁇ m after drying.
• PET polyethylene terephthalate
• the coated sheet was dried at 80 ° C. for 3 minutes, then transferred to both sides of a 2 ⁇ m thick PET film substrate, and aged at room temperature 23 ° C. and 50% humidity for 7 days to obtain a double-sided tape.
• Various properties of the obtained pressure-sensitive adhesive tape were measured and are shown in Table 1.
• Examples 2 to 4, Examples 6 to 8 and Comparative Examples 1 to 5 Performed in the same manner as in Example 1 except that the type of the (meth) acrylic polymer (A), the type of the synthetic hydrocarbon-based tackifying resin (B) and the amount used were changed as described in Table 1, and the pressure-sensitive adhesive composition was used. Products 2 to 4 and 6 to 13 were obtained. Various properties of the obtained pressure-sensitive adhesive tape were measured and are shown in Table 1.
• PSA composition 5 was obtained in the same manner as in Example 1, except that 0.2 parts by mass of a silane coupling agent (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts of the resin solids.
• KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.
• Example 9 The pressure-sensitive adhesive composition 1 was applied on a release-treated PET release film so as to have a thickness of 25 ⁇ m after drying.
• the coated sheet was dried at 80 ° C. for 3 minutes, transferred to a PET film substrate having a thickness of 25 ⁇ m, and aged at room temperature 23 ° C. and 50% humidity for 7 days to obtain a single-sided tape.
• Various properties of the obtained pressure-sensitive adhesive tape were measured and are shown in Table 2.
• Example 6 A single-sided tape was obtained in the same manner as in Example 9 except that the pressure-sensitive adhesive composition 13 was changed. Various properties of the obtained pressure-sensitive adhesive tape were measured and are shown in Table 2.
• the measurement method is described below.
• Weight average molecular weight (Mw) The weight average molecular weight (Mw) of the (meth) acrylic polymer (A) was determined by gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene.
• ⁇ Measuring device HLC-8120GPC (Tosoh Corporation) -GPC column configuration: The following five columns (all manufactured by Tosoh Corporation) (1) TSK-GELHXL-H (guard column) (2) TSK-GELG7000HXL (3) TSK-GELGMHXL (4) TSK-GELGMHXL (5) TSK-GELG 2500HXL Sample Concentration: As will be 1.0 mg / cm 3, diluting and mobile phase solvent with tetrahydrofuran: tetrahydrofuran Flow rate: 1.0 cm 3 / min -Column temperature: 40 ° C
• a test piece was obtained by peeling one PET release film, backing the exposed one pressure-sensitive adhesive layer surface with a 6 ⁇ m-thick PET film, and cutting the film into 25 mm ⁇ 70 mm.
• a test piece was obtained by simply cutting it into a size of 25 mm ⁇ 70 mm.
• the remaining PET release film was peeled off the test piece under the condition of 23 ° C. and 50% RH, and stainless steel (SUS) was bonded to the exposed pressure-sensitive adhesive layer surface using a 2 kg roller (bonding area 25 mm ⁇ 70 mm). . Twenty minutes after bonding, the test piece was peeled from the SUS plate in the direction of 180 ° at a speed of 300 mm / min, and the adhesive strength of the adhesive layer was measured.
• a test piece was obtained by peeling the PET release film on one side, backing the exposed one side of the pressure-sensitive adhesive layer with a PET film having a thickness of 100 ⁇ m, and cutting the film to a width of 20 mm.
• a test piece was obtained by simply cutting the tape to 20 mm. Thereafter, the PET release film on the other side was peeled off, the other exposed pressure-sensitive adhesive layer side was stuck on a SUS plate, and pressure-bonded using a 2 kg roller. The sticking area was 20 mm ⁇ 20 mm.
• nc means that the deviation amount is equal to or less than the lower limit of measurement.
• the PET release film remaining on the test piece was peeled off, bonded to a SUS plate whose surface was polished and cleaned with a solvent, and a load of 200 g was applied in the direction of 90 ° at a temperature of 80 ° C., and the peeling distance when left for 60 minutes (Mm) or the time to drop was measured.
• Mm 60 minutes
• X ′ ⁇ in the table means that the device has fallen within 60 minutes, and that it has fallen for “X” minutes.
• test piece In the case of a double-sided pressure-sensitive adhesive tape, one PET release film was peeled off, and a liner of a 6 ⁇ m-thick PET film was lined with the exposed one surface of the pressure-sensitive adhesive layer, and cut into a size of 20 mm ⁇ 50 mm to prepare a test piece.
• a test piece In the case of a single-sided tape, a test piece was prepared only by cutting into a size of 20 mm ⁇ 50 mm. The test piece was prepared by peeling off the PET release film of the test piece and bonding it to glass. After autoclaving the test piece (50 ° C., 5 atm, 20 minutes), the appearance of the test piece was visually evaluated. Colorless and transparent were evaluated as ⁇ , those with slight yellow transparency and white turbidity were evaluated as ⁇ , and those with clear color were evaluated as x.
• Comparative Examples 1 and 2 a rosin-based tackifying resin was used, and the adhesive strength, holding power, and constant load releasability were lower than those in Examples 1, 6, 7, and 8. Furthermore, in Comparative Example 2, since the amount of the tackifying resin added was equivalent to that of Examples 1, 6, 7, and 8, the compatibility was worse, the sheet appearance was poor, and the curved surface adhesion was reduced. In Comparative Example 3, the same synthetic hydrocarbon-based tackifying resin as in Example 1 was used, but the content of the synthetic hydrocarbon-based tackifying resin was (meth) acrylic polymer (A) and the synthetic hydrocarbon-based tackifying resin.
• Example 9 and Comparative Example 6 the pressure-sensitive adhesive composition used in Example 1 and Comparative Example 5 was applied to a single-sided tape. However, like Example 1 and Comparative Example 5, Comparative Example 6 As compared with Example 9, the adhesive strength, the holding power, and the constant load releasability were reduced.

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