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
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
  • C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• • 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
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • 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
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
• • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
• • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • 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]
• • 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
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • 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
  • C09J2423/00—Presence of polyolefin
• • 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
  • C09J2451/00—Presence of graft polymer

Definitions

• the present invention relates to an adhesive composition and an adhesive sheet.
• a laminate obtained by laminating a plurality of films or sheets is used.
• the laminate used for manufacturing flexible electronic devices in addition to the durability required for manufacturing conventional electronic devices, it is possible to suppress the occurrence of peeling or floating even when bent (that is, excellent bending resistance). ) Is required. Therefore, the pressure-sensitive adhesive composition used to form the laminate is required to have excellent adhesiveness and bending resistance.
• Patent Document 1 states that as a sealing material useful for manufacturing a flexible electronic device, a polyolefin resin and / or a polyolefin rubber, an inorganic filler, and a bidentate coordination in which both of the two coordination atoms are oxygen atoms.
• a sealing composition comprising a metal complex in which a monodentate ligand having a child and a coordinating atom of an oxygen atom bonded to a central metal is disclosed.
• Polyimide is often used as part of the laminate that constitutes a flexible electronic device. Therefore, there is a demand for an adhesive composition having excellent adhesiveness to polyimide (particularly adhesiveness at high temperature) and bending resistance.
• the present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition having excellent adhesiveness and bending resistance (particularly, adhesiveness to polyimide at high temperature and bending resistance). To do.
• the present invention that can achieve the above object is as follows. [1] (A) an isobutene-based polymer having a crosslinked structure formed by a reaction of an epoxy group with an acid anhydride group and / or a carboxy group, and (B) an alkoxide having a divalent or higher valent metal as a central metal.
• a pressure-sensitive adhesive composition comprising at least one selected from the group consisting of a carboxylate having a divalent or higher metal as a central metal and a chelate compound having a divalent or higher metal as a central metal.
• concentration of the structural unit derived from the alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms in the isobutylene polymer is 0.005 to 5 mmol / g.
• the isobutylene polymer is (A1) A reaction product of an isobutene-isoprene copolymer having an epoxy group and an olefin polymer having an acid anhydride group and / or a carboxy group, and (a2) an acid anhydride group and / or a carboxy group. At least one selected from the group consisting of a reaction product of an isobutene-isoprene copolymer having an epoxy group and an olefin-based polymer having an epoxy group, and at least one of the isobutene-isoprene copolymer and the olefin-based polymer.
• the metal having a divalent value or higher is aluminum, titanium or zirconium.
• an adhesive composition having excellent adhesiveness and bending resistance (particularly, adhesiveness and bending resistance at high temperature to polyimide).
• the pressure-sensitive adhesive composition of the present invention (A) an isobutene-based polymer having a crosslinked structure formed by a reaction between an epoxy group and an acid anhydride group and / or a carboxy group, and (B) an alkoxide having a divalent or higher valent metal as a central metal and divalent or higher.
• the isobutene-based polymer contains at least one selected from the group consisting of a carboxylate compound of the metal of the above and a chelate compound of a metal having a valence of 2 or more, and the isobutene-based polymer has an alkyl group having 6 or more carbon atoms as a side chain. It is characterized by having a polymer chain containing a structural unit derived from (meth) acrylate.
• alkyl (meth) acrylate means “alkyl acrylate or alkyl methacrylate”. Both alkyl acrylates and alkyl methacrylates may be used.
• the carbon number of the alkyl group in the above-mentioned "alkyl (meth) acrylate having an alkyl group” needs to be 6 or more from the viewpoint of adhesiveness.
• the carbon number is preferably 7 or more, more preferably 8 or more.
• the upper limit of the carbon number is not particularly limited, but the carbon number is preferably 30 or less, more preferably 24 or less, and more, from the viewpoint of lowering the glass transition point of the pressure-sensitive adhesive composition so as to be suitable for flexible electronic device applications. It is more preferably 22 or less, still more preferably 20 or less, even more preferably 18 or less, particularly preferably 16 or less, particularly more preferably 14 or less, and most preferably 12 or less.
• the alkyl group may be linear or branched.
• alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms is abbreviated as “long-chain alkyl (meth) acrylate”
• a structural unit derived from long-chain alkyl (meth) acrylate May be abbreviated as “long-chain alkyl (meth) acrylate unit”.
• other structural units may be abbreviated in the same manner.
• polymer chain containing long-chain alkyl (meth) acrylate unit may be abbreviated as “long-chain alkyl (meth) acrylate polymer chain”, and "epoxide group and acid anhydride group and / Alternatively, a crosslinked isobutene having a long-chain alkyl (meth) acrylate polymer chain as a side chain and an isobutene-based polymer having a crosslinked structure formed by a reaction with a carboxy group and a long-chain alkyl (meth) acrylate polymer chain as a side chain. It may be abbreviated as "system polymer”.
• the "crosslinked isobutene-based polymer having a long-chain alkyl (meth) acrylate polymer chain” is referred to as "(A) component” and "(B) an alkoxide having a divalent or higher valent metal as a central metal, 2 "At least one selected from the group consisting of a carboxylate compound of a metal having a valence or higher and a chelate compound of a metal having a valence of 2 or higher” may be described as “component (B)".
• the adhesiveness to polyimide at high temperature can be improved.
• the mechanism is that the component (A) has a long-chain alkyl (meth) acrylate polymer chain, so that the cohesive force of the component (A) is improved, and as a result, the adhesive composition containing the component (A) is adhered. It is estimated that the sex will improve.
• the present invention is not limited to such an estimation mechanism.
• bending resistance can be improved by using the component (A) and the component (B) in combination.
• the mechanism is that the carboxy group and / or the hydroxy group in the component (A) formed by the reaction of the epoxy group with the acid anhydride group and / or the carboxy group is crosslinked with the component (B). It is presumed that the bending resistance of the pressure-sensitive adhesive composition containing the component (A) and the component (B) is improved.
• the present invention is not limited to such an estimation mechanism.
• each component only one kind may be used, or two or more kinds may be used in combination.
• the pressure-sensitive adhesive composition of the present invention contains a crosslinked isobutylene polymer (component (A)) having a long-chain alkyl (meth) acrylate polymer chain.
• the side chain ie, the long-chain alkyl (meth) acrylate polymer chain
• the copolymer may be a block polymer or a random copolymer.
• the crosslinked structure in the component (A) is preferably formed by the reaction of an epoxy group and an acid anhydride group.
• the component (A) may contain only one type of long-chain alkyl (meth) acrylate unit, or may contain two or more types of long-chain alkyl (meth) acrylate units.
• the long-chain alkyl (meth) acrylate include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecylic (meth) acrylate, and dodecyl (meth) acrylate ( Also known as: lauryl (meth) acrylate) and the like.
• 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate are preferable, and 2-ethylhexyl acrylate and lauryl methacrylate are more preferable.
• the concentration of the long-chain alkyl (meth) acrylate unit in the component (A) is preferably 0.005 to 5 mmol / g, more preferably 0.007 to 3 mmol / g, still more preferably 0.01 to 1 mmol / g. be.
• concentration of the long-chain alkyl (meth) acrylate unit in the component (A) means the amount (mmol) of the long-chain alkyl (meth) acrylate unit per 1 g of the component (A). Concentrations in other units have the same meaning.
• the concentration of the long-chain alkyl (meth) acrylate unit in the component (A) is, for example, the long-chain alkyl (meth) in the raw material of the component (A) (for example, an isobutylene-isoprene copolymer having an epoxy group described later). ) It can be calculated from the concentration of acrylate units. Further, the concentration of the long-chain alkyl (meth) acrylate unit in the raw material of the component (A) can be calculated from the monomer usage fee at the time of its synthesis.
• the "isobutene-based polymer” is a structural unit derived from isobutene (hereinafter sometimes abbreviated as “isobutene unit”), which is the main structural unit (that is, the total amount of isobutene units is the total composition). It means a polymer (which is the largest in the unit).
• the isobutene-based polymer is preferably an isobutene-isoprene copolymer (that is, butyl rubber).
• the component (A) is (A1) A reaction product of an isobutene-isoprene copolymer having an epoxy group and an olefin polymer having an acid anhydride group and / or a carboxy group (hereinafter, referred to as “reaction product (a1)”). (A2) and (a2) a reaction product of an isobutene-isoprene copolymer having an acid anhydride group and / or a carboxy group and an olefin polymer having an epoxy group (hereinafter referred to as “reaction product (a2)").
• At least one selected from the group consisting of, and at least one of the isobutene-isoprene copolymer and the olefin-based polymer has a long-chain alkyl (meth) acrylate polymer chain as a side chain.
• the "olefin polymer” is mainly composed of a structural unit derived from an olefin (hereinafter, may be abbreviated as “olefin unit”) (that is, the amount of the olefin unit is the total structural unit). Means the polymer (which is the largest of all).
• olefin a monoolefin having one olefinic carbon-carbon double bond and / or a diolefin having two olefinic carbon-carbon double bonds are preferable.
• the monoolefin include ⁇ -olefins such as ethylene, propylene, 1-butene, isobutene (isobutylene), 1-pentene, 1-hexene, 1-heptene and 1-octene.
• diolefin include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene and the like.
• the olefin polymer may be a homopolymer or a copolymer.
• the copolymer may be a random copolymer or a block copolymer.
• the olefin-based polymer may be a copolymer of an olefin and a monomer other than the olefin.
• the isobutene-isoprene copolymer and the olefin-based polymer may be used alone or in combination of two or more.
• the acid anhydride group and / or the carboxy group is preferably an acid anhydride group.
• the olefin-based polymer is preferably an isobutene-based polymer, and more preferably an isobutene-isoprene copolymer (that is, butyl rubber).
• the concentration of the epoxy group in the isobutene-isoprene copolymer having an epoxy group and the concentration of the epoxy group in the olefin-based polymer having an epoxy group are independent of each other, preferably 0.01 to. It is 10 mmol / g, more preferably 0.05 to 5 mmol / g. This epoxy group concentration is obtained from the epoxy equivalent obtained based on JIS K 7236-1995.
• the concentration of the acid anhydride group in the isobutene-isoprene copolymer having an acid anhydride group and the concentration of the acid anhydride group in the olefin polymer having an acid anhydride group are independent of each other. Therefore, it is preferably 0.01 to 10 mmol / g, and more preferably 0.05 to 5 mmol / g.
• the concentration of the acid anhydride group is determined from the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the resin according to the description of JIS K2501.
• the concentration of the carboxy group in the isobutene-isoprene copolymer having a carboxy group and the concentration of the carboxy group in the olefin polymer having a carboxy group are independent and preferably 0.01. It is ⁇ 10 mmol / g, more preferably 0.05 ⁇ 5 mmol / g.
• the concentration of the carboxy group is determined from the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the resin according to the description of JIS K2501.
• the sum of the concentration of the acid anhydride group and the concentration of the carboxy group in the isobutene-isoprene copolymer having the acid anhydride group and the carboxy group that is, “concentration of the acid anhydride group + carboxy group”.
• Concentration and the sum of the concentration of the acid anhydride group and the concentration of the carboxy group in the olefin polymer having the acid anhydride group and the carboxy group are independently, preferably 0.01 to 10 mmol / g, respectively. More preferably, it is 0.05 to 5 mmol / g.
• the number average molecular weight of the isobutene-isoprene copolymer having an epoxy group (hereinafter, may be referred to as “Mn”), the Mn of the olefin polymer having an acid anhydride group and / or the carboxy group.
• the Mn of the isobutene-isoprene copolymer having an acid anhydride group and / or the carboxy group and the Mn of the olefin polymer having an epoxy group are independently, preferably 1,000 to 1,000,000. It is more preferably 20,000 to 500,000, still more preferably 50,000 to 500,000.
• Mn in this specification is a value measured by a gel permeation chromatography (GPC) method (polystyrene conversion).
• GPC gel permeation chromatography
• the number average molecular weight by the GPC method is "LC-9A / RID-6A” manufactured by Shimadzu Corporation as a measuring device and "Shodex K-800P / K-804L / K-804L” manufactured by Showa Denko Corporation as a column.
• the amount of the isoprene unit in the component (A) is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and further 0, based on the total of the isobutene unit and the isoprene unit. .5 to 10% by mass.
• the ratio to the amount (mol) is preferably 100:20 to 100: 1,000, more preferably 100:30. It is ⁇ 100: 400, more preferably 100: 50-100: 300.
• the ratio to mol) (that is, "amount of epoxy group (mol): amount of carboxy group (mol)") is preferably 100:20 to 100: 1,000, more preferably 100:30 to 100:400. , More preferably 100: 50 to 100: 300.
• the ratio of the amount of the physical group (mol) and the total amount of the carboxy group (mol) that is, “amount of epoxy group (mol): (amount of acid anhydride group (mol) + amount of carboxy group (mol)) ) ”)
• the “amount of epoxy group (mol): amount of acid anhydride group (mol)” for forming the reaction product (a2) is the corresponding preferable range described in the reaction product (a1) (that is, that is, It is the same as the preferable range of "amount of epoxy group (mol): amount of acid anhydride group (mol)” for forming the reaction product (a1)).
• the preferred range of “group amount (mol))” is also the same as the corresponding preferred range described in the reaction product (a1), respectively.
• the component (A) is (A3) Reaction of an isobutene-isoprene copolymer having a polymer chain containing an epoxy group and a long-chain alkyl (meth) acrylate unit as a side chain with an olefin polymer having an acid anhydride group and / or a carboxy group.
• reaction product (a3) Reaction product (A4) Reaction of an isobutene-isoprene copolymer having a polymer chain containing an acid anhydride group and / or a carboxy group and a long-chain alkyl (meth) acrylate unit as a side chain with an olefin polymer having an epoxy group.
• Isobutene-isoprene co-weight having a product hereinafter sometimes referred to as “reaction product (a4)
• reaction product (a5) a polymer chain containing an epoxy group and a long-chain alkyl (meth) acrylate unit as a side chain.
• reaction product (a5) At least one selected from the group consisting of.
• the isobutene-isoprene copolymer and the olefin-based polymer may be used alone or in combination of two or more.
• the component (A) is preferably at least one selected from the group consisting of the reaction product (a3) and the reaction product (a4).
• the acid anhydride group and / or the carboxy group is preferably an acid anhydride group.
• the olefin-based polymer is preferably an isobutene-based polymer, and more preferably an isobutene-isoprene copolymer (that is, butyl rubber).
• Examples of the isobutene-isoprene copolymer having a polymer chain containing an epoxy group and a long-chain alkyl (meth) acrylate unit as a side chain include a copolymer of an epoxy group-containing unsaturated compound and a long-chain alkyl (meth) acrylate.
• Examples thereof include butyl rubber modified by coalescence (that is, an isobutene-isoprene copolymer).
• butyl rubber modified by a copolymer means “butyl rubber having the copolymer chain as a side chain”.
• This "copolymer-modified butyl rubber” and the like may be referred to as “copolymer-modified butyl rubber” and the like in the present specification.
• the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether.
• the epoxy group-containing unsaturated compound only one kind may be used, or two or more kinds may be used in combination.
• the epoxy group-containing unsaturated compound is preferably glycidyl (meth) acrylate.
• Examples of the isobutene-isoprene copolymer having a polymer chain containing an acid anhydride group and / or a carboxy group and a long-chain alkyl (meth) acrylate unit as a side chain include a carboxylic acid anhydride and a long-chain alkyl (meth) acrylate.
• Butyl rubber modified by the copolymer with (that is, isobutene-isoprene copolymer) and the like can be mentioned.
• Examples of the carboxylic acid anhydride include succinic anhydride, maleic anhydride, glutaric anhydride and the like. As the carboxylic acid anhydride, only one kind may be used, or two or more kinds may be used in combination.
• the carboxylic acid anhydride is preferably maleic anhydride.
• the epoxy group-containing unsaturated compound-long-chain alkyl (meth) acrylate copolymer-modified butyl rubber used in the aspect (2) is, for example, a monomer (that is, an epoxy group-containing unsaturated compound and a long-chain alkyl (meth)) in a butyl rubber. It can be produced by grafting an unsaturated compound containing an epoxy group (acrylate) or a long-chain alkyl (meth) acrylate copolymer. Carboxylic acid anhydride-long-chain alkyl (meth) acrylate copolymer-modified butyl rubber and the like can also be produced in the same manner. Further, these modified butyl rubbers and the like can be obtained from, for example, Seiko PMC.
• the olefin-based polymer having an acid anhydride group and / or a carboxy group used in the embodiment (1) or (2) is an acid. It can be produced by graft-modifying an olefin polymer with an unsaturated compound having an anhydride group and / or a carboxy group (for example, maleic anhydride) under radical reaction conditions.
• the olefin-based polymer having an acid anhydride group and / or a carboxy group used in the embodiment (1) or (2) for example, the following can be obtained.
• the isobutene-isoprene copolymer having an acid anhydride group and / or a carboxy group include “ER661” (maleic anhydride-butyl methacrylate random copolymer modified butyl rubber) manufactured by Seiko PMC Corporation.
• Examples of the olefin polymer having an acid anhydride group and / or a carboxy group include “HV-300M” (maleic anhydride-modified polybutene) manufactured by Toho Chemical Industry Co., Ltd. "T-YP279” (maleic anhydride-modified propylene-buten random copolymer) manufactured by Seikou PMC, “T-YP312” (maleic anhydride-modified propylene-buten random copolymer) manufactured by Seikou PMC, manufactured by Mitsui Kagaku Co., Ltd.
• Examples thereof include “Lucant A-5260” (maleic anhydride-modified ethylene- ⁇ -olefin random copolymer) and “Lucant A-5320” (maleic anhydride-modified ethylene- ⁇ -olefin random copolymer).
• the olefin-based polymer having an epoxy group (for example, an isobutene-isoprene copolymer having an epoxy group) used in the embodiment (1) or (2) is an epoxy group-containing unsaturated compound (for example, glycidyl (meth) acrylate, 4-Hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether) can be produced by graft-modifying an olefin polymer under radical reaction conditions.
• an epoxy group-containing unsaturated compound for example, glycidyl (meth) acrylate, 4-Hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether
• the olefin-based polymer having an epoxy group used in the embodiment (1) or (2) for example, the following can be obtained.
• the isobutylene-isoprene copolymer having an epoxy group include "ER866” (glycidyl methacrylate-modified butyl rubber) manufactured by Seiko PMC and "ER850” (glycidyl methacrylate-modified butyl rubber) manufactured by Seiko PMC.
• Examples of the olefin polymer having an epoxy group include “T-YP341” (glycidyl methacrylate-modified propylene-butene random copolymer) manufactured by Seikou PMC, and Seikou PMC. Examples thereof include “T-YP276” (glycidylmethacrylate-modified propylene-butenerandom copolymer) manufactured by Seikou PMC and "T-YP313” (glycidylmethacrylate-modified propylene-butenerandom copolymer) manufactured by Seikou PMC.
• the content of the component (A) in the pressure-sensitive adhesive composition is preferably 10% by mass or more, more preferably 20% by mass or more, based on 100% by mass of the non-volatile content of the pressure-sensitive adhesive composition from the viewpoint of adhesiveness and bending resistance. It is more preferably 30% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less.
• the pressure-sensitive adhesive composition of the present invention is an alkoxide having a divalent or higher metal (hereinafter, may be simply abbreviated as "metal”) as a central metal (hereinafter, may be referred to as “metal alkoxide”), and is divalent.
• metal alkoxide a divalent or higher metal
• metal alkoxide a central metal
• metal alkoxide a central metal
• Carboxylates having the above metals as the central metal hereinafter sometimes referred to as "metal carboxylates”
• chelate compounds having a divalent or higher metal as the central metal
• the "metal alkoxide” means a compound containing a structure represented by M-OR (in the above formula, M indicates a metal having a valence of 2 or more and R indicates an organic group).
• Metal alkoxide means a compound containing a structure represented by MO- (CO) -R (in the above formula, M indicates a metal having a valence of 2 or more, and R indicates an organic group).
• MO- (CO) -R in the above formula, M indicates a metal having a valence of 2 or more, and R indicates an organic group).
• the "metal chelate compound” means a compound containing a chelate ring structure formed by binding a polydentate ligand to a central metal which is a divalent or higher metal.
• a compound having a chelate ring structure and a structure represented by M-OR or MO- (CO) -R is classified as a "metal chelate compound" in the present invention.
• the metal having a valence of 2 or more is preferably a metal of Group 4 of the periodic table or a metal of Group 13 of the periodic table, and more preferably aluminum, titanium or zirconium.
• polydentate ligand that can be used to form a metal chelate compound, for example, the following formula (a):
• Compound (a) represents a polydentate ligand before coordination with the central metal.
• the polydentate ligand coordinated to the central metal and the polydentate ligand before coordination to the central metal are referred to as "polydentate ligand" without particular distinction. May be referred to.
• the specific example of the compound represented by the formula (a) is synonymous with the specific example of the polydentate ligand in the compound represented by the formula (1) described later.
• the component (B) is preferably the following formula (1):
• M represents a metal having a valence of 2 or more.
• R 1 and R 3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkenyloxy group, an aryl group, or an aralkyl group, respectively.
• R 2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkenyloxy group, an alkoxycarbonyl group, an aryl group, or an aralkyl group.
• X represents a monodentate ligand and represents The solid line between the oxygen atom (O) and M in [] in equation (1) represents a covalent bond.
• the dashed line between the oxygen atom (O) and M in [] in equation (1) represents a coordination bond, and m represents 3 or 4, and n represents an integer from 0 to 4. m ⁇ n. ]
• metal complex (1) a metal complex represented by (hereinafter, may be abbreviated as "metal complex (1)").
• metal complex (1) only one kind may be used, or two or more kinds may be used in combination.
• examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group may be either linear or branched.
• the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6.
• Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and a 1-ethylpropyl group.
• Examples thereof include a hexyl group, an isohexyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group and a 2-ethylbutyl group.
• the alkyl group may have a substituent.
• the substituent include a halogen atom, a hydroxy group, an amino group which may have a substituent, and the like.
• the alkenyl group may be linear or branched.
• the alkenyl group preferably has 2 to 20 carbon atoms.
• Examples of the alkenyl group include an ethenyl group (that is, a vinyl group), a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group and a 3-butenyl group.
• 3-Methyl-2-butenyl group 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5- Examples include a hexenyl group.
• the alkenyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an amino group which may have a substituent, and the like.
• the alkynyl group may be linear or branched.
• the alkynyl group has preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentynyl group, a 2-pentynyl group and a 3-pentynyl group.
• Examples thereof include 4-pentynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 4-methyl-2-pentynyl group and the like.
• the alkynyl group may have a substituent.
• the substituent include a halogen atom, a hydroxy group, an amino group which may have a substituent, and the like.
• the aryl group has preferably 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms.
• the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group and the like.
• the aryl group may have a substituent.
• the substituent include a halogen atom, a hydroxy group, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and an alkynyl group which may have a substituent. Examples thereof include an amino group which may have a substituent.
• the carbon number of the aralkyl group is preferably 7 to 16.
• the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a phenylpropyl group and the like.
• the aralkyl group may have a substituent.
• the substituent include a halogen atom, a hydroxy group, an amino group which may have a substituent, and the like.
• examples of the amino group which may have a substituent include an amino group, a mono- or di-alkylamino group (eg, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, etc.
• Propylamino group, dibutylamino group mono- or di-cycloalkylamino group (eg, cyclopropylamino group, cyclohexylamino group), mono- or di-arylamino group (eg, phenylamino group), mono- or Examples thereof include a di-aralkylamino group (eg, benzylamino group, dibenzylamino group), a heterocyclic amino group (eg, pyridylamino group) and the like.
• a di-aralkylamino group eg, benzylamino group, dibenzylamino group
• a heterocyclic amino group eg, pyridylamino group
• the description of the alkyl group in the alkoxy group (that is, the alkyloxy group) is the same as the description of the above-mentioned alkyl group.
• the alkoxy group may have a substituent.
• the substituent include a halogen atom, a hydroxy group, an amino group which may have a substituent, and the like.
• the alkenyloxy group may have a substituent.
• substituent include a halogen atom, a hydroxy group, an amino group which may have a substituent, and the like.
• the description of the alkyl group in the alkoxycarbonyl group (that is, the alkyloxycarbonyl group) is the same as the description of the above-mentioned alkyl group.
• the alkoxycarbonyl group may have a substituent.
• the substituent include a halogen atom, a hydroxy group, an amino group which may have a substituent, and the like.
• Examples of the monodentate ligand represented by X include an alkoxide anion (RO ⁇ ) (in the above formula, R indicates an organic group) and a carboxylate anion (RCOO ⁇ ) (in the above formula, R is an organic group). Shown), oxo (O) and the like.
• RO ⁇ alkoxide anion
• RCOO ⁇ carboxylate anion
• O oxo
• the alkoxide anion is represented by RO- ( in the above formula, R represents an organic group).
• the organic group R may be either an aliphatic group or an aromatic group. Further, the aliphatic group may be either a saturated aliphatic group or an unsaturated aliphatic group.
• the organic group R preferably has 1 to 20 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 8 to 14 carbon atoms.
• alkoxide anion examples include methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, sec-butoxide, tert-butoxide, pentyl oxide, hexyl oxide, phenoxide, 4-methylphenoxide and the like. Be done.
• the carboxylate anion is represented by RCOO ⁇ (in the above formula, R indicates an organic group).
• the organic group R may be either an aliphatic group or an aromatic group. Further, the aliphatic group may be either a saturated aliphatic group or an unsaturated aliphatic group.
• the organic group R preferably has 1 to 20 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 8 to 14 carbon atoms.
• Examples of the carboxylate anion (RCOO- ) include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, octyl acid, nonanoic acid, decanoic acid, dodecanoic acid, stearic acid, and oleic acid.
• Examples thereof include carboxylate anions corresponding to carboxylic acids such as linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid and benzoic acid.
• Examples of the polydentate ligand in the formula [] represent acetylacetone, 3-methyl-2,4-pentandione, acetylacetoaldehyde, 2,4-hexanedione, 2, 4-Heptanedione, 5-methyl-2,4-hexanedione, 5,5-dimethyl-2,4-hexanedione, benzoylacetone, benzoylacetophenone, salicylaldehyde, 1,1,1-trifluoroacetylacetone, 1, 1,1,5,5,5-hexafluoroacetylacetone, 3-methoxy-2,4-pentandione, 3-cyano-2,4-pentandione, 3-nitro-2,4-pentandione, 3-chloro -2,4-Pentandione, acetoacetic acid, methyl acetoacetate, ethyl acetoacetate, propylacetoacetate, salicylic acid, methyl salicylate, mal
• metal complex (1) in which M is aluminum examples include aluminum diisopropyrate monosec-butyrate, aluminum trisec-butyrate, aluminum triisopropylate, aluminum triethylate, aluminum tris (acetylacetonate), and aluminum.
• metal complex (1) in which M is titanium examples include tetraisopropyl titanate, tetranormal butyl titanate, tetraoctyl titanate, tetratert-butyl titanate, tetrastearyl titanate, titanium tetraacetylacetonate, and titanium octylene glycolate.
• titanium diisopropoxide bis ethylacetate acetate
• allylacetacetate triisopropoxide titanium di Normalbutoxide bis (2,4-pentandionate), Titanium diisopropoxide bis (Tetramethylheptandionate), Titanium diisopropoxidebis (Ethylacetacetate), Titanium (IV) Tetra (Methylphenorate)
• titanium oxide bis (2,4-pentanionate) monoisopropoxytitanium triisostearate, and diisopropoxytitanium diisosteare.
• metal complex (1) in which M is zirconium examples include zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetra (acetylacetonate), zirconium allylacetacetate triisopropoxide, and zirconium dinormalbutoxide bis (zirconium dinormalbutoxide bis).
• the component (B) is M is aluminum, titanium or zirconium
• One of R 1 and R 3 is an alkyl group, an alkoxy group or an alkenyloxy group, and the other one is an alkyl group.
• R 2 is a hydrogen atom
• X is an alkoxide anion or a carboxylate anion
• m is 3 or 4
• n is an integer of 1 to 3
• m> n is a metal complex (1).
• M is preferably aluminum or zirconium.
• the description (preferable carbon number, example, etc.) of the alkyl group, the alkoxy group or the alkenyloxy group, the alkoxide anion and the carboxylate anion in the aspect (3) is as described above.
• the component (B) is a specific example of the above-mentioned metal complex (1) in which M is aluminum, and the metal complex (1) in which M is titanium. ), And at least one selected from the group consisting of the specific examples of the metal complex (1) in which M is zirconium.
• the component (B) is preferably selected from the group consisting of the above-mentioned specific examples of the metal complex (1) in which M is aluminum and the specific example of the metal complex (1) in which M is zirconium.
• the content of the component (B) in the pressure-sensitive adhesive composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, based on 100% by mass of the non-volatile content of the pressure-sensitive adhesive composition from the viewpoint of bending resistance. Yes, preferably 15% by mass or less, more preferably 10% by mass or less.
• the pressure-sensitive adhesive composition of the present invention may further contain (C) a liquid polyolefin resin and / or a liquid rubber (which may be referred to as “component (C)" in the present specification).
• component (C) a liquid polyolefin resin and / or a liquid rubber
• “liquid” means that the viscosity at 25 ° C. is 5,000 Pa ⁇ s or less.
• the "viscosity at 25 ° C.” means the viscosity calculated by multiplying the kinematic viscosity at 25 ° C. measured by the dynamic viscoelasticity measuring device by the density. Examples of the dynamic viscoelasticity measuring device include a leometer manufactured by TA Instruments (trade name: DISCOVERY HR-2).
• the "liquid polyolefin resin” means an olefin polymer having a viscosity at 25 ° C. of 5,000 Pa ⁇ s or less and which cannot form a rubber elastic body by cross-linking.
• the "liquid rubber” means a rubber having a viscosity at 25 ° C. of 5,000 Pa ⁇ s or less and capable of forming a rubber elastic body by cross-linking.
• liquid polyisoprene is classified as liquid rubber because it can form a rubber elastic body by cross-linking.
• the viscosities of the liquid polyolefin resin and the liquid rubber at 25 ° C. are preferably 5 to 5,000 Pa ⁇ s, more preferably 10 to 4,000 Pa ⁇ s, and further preferably 20 to 3,000 Pa ⁇ s, respectively. ..
• the number average molecular weight of the liquid polyolefin resin is preferably 500 to 40,000, more preferably 750 to 35,000, and even more preferably 1,000 to 30,000.
• the number average molecular weight of the liquid rubber is 500 to 40,000, more preferably 750 to 35,000, and even more preferably 1,000 to 30,000.
• the liquid polyolefin resin and / or liquid rubber is preferably liquid polybutene.
• the liquid polybutene may be a homopolymer (for example, 1-butene homopolymer, isobutene homopolymer) or a copolymer (for example, a copolymer of 1-butene and isobutene).
• liquid polyolefin resin examples include "HV-300” (liquid polybutene) manufactured by ENEOS, "HV-1900” (liquid polybutene) manufactured by ENEOS, and "HV-50” (liquid polybutene) manufactured by ENEOS.
• liquid rubber products include, for example, "Poly bd R-45HT” (butadiene liquid rubber) manufactured by Idemitsu Showa Shell, “Poly bd R-15HT” (butadiene liquid rubber) manufactured by Idemitsu Showa Shell, and Idemitsu Showa.
• its content in the pressure-sensitive adhesive composition is preferably 5% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the non-volatile content of the pressure-sensitive adhesive composition from the viewpoint of adhesion and bending resistance. Is 10% by mass or more, more preferably 15% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less.
• the pressure-sensitive adhesive composition may contain components other than the components (A) to (C) (hereinafter, may be referred to as "other components") as long as the effects of the present invention are not impaired.
• other components include curing accelerators, tackifiers, inorganic or organic fillers, antioxidants, plasticizers and the like. In each of these, only one kind may be used, or two or more kinds may be used in combination.
• a curing accelerator as another component.
• the curing accelerator include imidazole compounds, tertiary and quaternary amine compounds, dimethylurea compounds, organic phosphine compounds and the like.
• imidazole compound examples include 1H-imidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and 2-un.
• Decylimidazole 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-phenyl-4,5-bis (hydroxymethyl) imidazole, 1-benzyl-2-methylimidazole , 1-benzyl-2-phenylimidazole, 2-phenylimidazole, 2-dodecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the like. ..
• imidazole compound examples include curesol 2MZ, 2P4MZ, 2E4MZ, 2E4MZ-CN, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2PHZ, 1B2MZ, 1B2PZ, 2PZ, C17Z, 1.2DMZ, 2P4MHZ-PW. , 2MZ-A, 2MA-OK (both manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like.
• the tertiary / quaternary amine-based compound is not particularly limited, and is, for example, a quaternary ammonium salt such as tetramethylammonium bromide, tetrabutylammonium bromide, triethylmethylammonium / 2-ethylhexanoate; DBU (1, 8-diazabicyclo [5.4.0] undecene-7), DBN (1,5-diazabicyclo [4.3.0] nonen-5), DBU-phenol salt, DBU-octylate, DBU-p-toluene Diazabicyclo compounds such as sulfonate, DBU-gerate, DBU-phenol novolak resin salt; benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol (TAP), etc. 3rd amines or salts thereof, dimethylurea compounds such as aromatic dimethylure
• dimethylurea compound examples include aromatic dimethylurea such as DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro); U-CAT3503N (manufactured by San-Apro). ) And the like, and examples thereof include aliphatic dimethylurea. Among them, aromatic dimethylurea is preferably used from the viewpoint of curability.
• organic phosphine compound examples include triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate, and (4-methylphenyl) triphenylphosphonium thiocyanate. Examples thereof include tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, triphenylphosphine triphenylborane and the like. Specific examples of the organic phosphine compound include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, TPP-S (all manufactured by Hokuko Chemical Industry Co., Ltd.) and the like.
• the content in the pressure-sensitive adhesive composition is for promoting the formation of the component (A) (that is, a crosslinked isobutene-based polymer having a long-chain alkyl (meth) acrylate polymer chain).
• component (A) that is, a crosslinked isobutene-based polymer having a long-chain alkyl (meth) acrylate polymer chain.
• 100% by mass of the non-volatile content of the pressure-sensitive adhesive composition it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 2% by mass.
• it is more preferably 1% by mass or less, still more preferably 0.5% by mass or less.
• Isobutene-based polymer "ER669” having a long-chain alkyl (meth) acrylate polymer chain and an acid anhydride group manufactured by Seikou PMC, maleic anhydride-2-ethylhexyl acrylate random copolymer-modified butyl rubber (1-2) Hereinafter referred to as "MA + 2-EHA modified IIR"
• concentration of long-chain alkyl (meth) acrylate unit 0.21 mmol / g
• acid anhydride group concentration 0.43 mmol / g
• number average molecular weight 96.
• Isobutene-based polymer "ER866” having an epoxy group or an acid anhydride group manufactured by Seikou PMC, glycidyl methacrylate-modified butyl rubber (hereinafter, may be referred to as "GMA-modified IIR", epoxy group concentration: 1.63 mmol / g, number average molecular weight: 113,000, isobutene unit / isoprene unit: 98.9% / 1.1%)
• GMA-modified IIR glycidyl methacrylate-modified butyl rubber
• MA + BMA modified IIR concentration of butyl methacrylate unit: 0.32 mmol / g, acid anhydrous Material concentration: 0.32 mmol / g, number average molecular weight: 40,000, isobutene unit / isoprene unit: 98.9%
• Example 1 A varnish with the compounding ratio shown in the table below was prepared by the following procedure, and an adhesive sheet was prepared using the obtained varnish.
• the amount (part) of each component shown in the table below indicates the amount of the non-volatile content of each component in the varnish.
• glycidyl methacrylate-2-ethylhexyl acrylate random copolymer-modified butyl rubber (“ER869” manufactured by Starlight PMC), maleic anhydride-2-ethylhexyl acrylate random copolymer-modified butyl rubber (“ER669” manufactured by Starlight PMC).
• Polybutene (“HV-1900” manufactured by ENEOS), a chelate compound of aluminum (“Plenact AL-M” manufactured by Ajinomoto Fine Techno Co., Ltd.), and a curing accelerator (“U CAT18X” manufactured by Sun Apro Co., Ltd.) were blended to obtain the obtained product.
• the mixture was evenly dispersed with a high speed rotary mixer to obtain a varnish of the adhesive composition.
• the obtained varnish was placed on a mold release-treated surface of a polyethylene terephthalate (PET) film (“SP3000” manufactured by Toyo Cloth Co., Ltd., PET film thickness: 38 ⁇ m) treated with a silicone-based mold release agent using a die coater. It was uniformly applied and heated at 130 ° C. for 30 minutes to obtain a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive composition layer having a thickness of 50 ⁇ m.
• PET polyethylene terephthalate
• Example 2 Maleic anhydride-2-ethylhexyl acrylate random copolymer-modified butyl rubber (“ER869” manufactured by Starlight PMC) was added to glycidyl methacrylate-lauryl methacrylate random copolymer-modified butyl rubber (“ER872" manufactured by Starlight PMC) and maleic anhydride-2. Examples except that the ethylhexyl acrylate random copolymer-modified butyl rubber (“ER669” manufactured by Starlight PMC) was changed to maleic anhydride-lauryl methacrylate random copolymer-modified butyl rubber (“ER674” manufactured by Starlight PMC). In the same manner as in No. 1, a varnish of the pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive composition layer having a thickness of 50 ⁇ m were prepared.
• Example 3 The same method as in Example 1 except that the glycidyl methacrylate-modified butyl rubber (“ER869” manufactured by Seiko PMC) was replaced with the glycidyl methacrylate-modified butyl rubber (“ER866” manufactured by Seiko PMC).
• ER869 glycidyl methacrylate-modified butyl rubber
• ER866 manufactured by Seiko PMC
• Example 4> Other than changing maleic anhydride-butyl methacrylate random copolymer-modified butyl rubber (Seikou PMC “ER669”) to maleic anhydride-butyl methacrylate random copolymer-modified butyl rubber (Seikou PMC “ER661”) Made a varnish of the pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive composition layer having a thickness of 50 ⁇ m by the same method as in Example 1.
• Example 5 The method is the same as in Example 1 except that the aluminum chelate compound (Ajinomoto Fine Techno Co., Ltd. "Plenact AL-M”) is changed to the zirconium chelate compound (Matsumoto Fine Chemical Co., Ltd. "Organtics ZC-540").
• a varnish of the pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive composition layer having a thickness of 50 ⁇ m were prepared.
• maleic anhydride-butyl methacrylate random copolymer-modified butyl rubber means “butyl rubber having maleic anhydride-butyl methacrylate random copolymer chain as a side chain”.
• the pressure-sensitive adhesive composition layer of Comparative Example 1 formed from “glycidyl methacrylate-2-ethylhexyl acrylate random copolymer-modified butyl rubber and maleic anhydride-butyl methacrylate random copolymer-modified butyl rubber.
• Cross-linked polymer is described as "(A') component”
• Constituent unit derived from butyl methacrylate is described as “butyl methacrylate unit”
• polymer chain containing butyl methacrylate unit is described as “butyl”.
• Lamination was performed under the conditions of a temperature of 80 ° C., a time of 30 seconds and a pressure of 0.3 MPa.
• the support (PET film) was peeled off from the obtained laminate, and a polyimide film (“UPIREX-S” manufactured by Ube Kosan Co., Ltd., thickness: 50 ⁇ m) was placed on the exposed adhesive composition layer under the same conditions as above.
• UPIREX-S manufactured by Ube Kosan Co., Ltd., thickness: 50 ⁇ m
• the "composite film / adhesive composition layer” was peeled off from the polyimide film at room temperature in a direction of 180 degrees with respect to the length direction of the PET film of the composite film and a tensile speed of 300 mm / min.
• the adhesive strength normal temperature adhesive strength
• the adhesive strength high-temperature adhesive strength
• the adhesiveness of the adhesive composition at high temperature was evaluated according to the following criteria. (Adhesion at high temperature) ⁇ (Very good): High temperature adhesive strength is 0.60 kgf / cm or more ⁇ (Good): High temperature adhesive strength is 0.55 kgf / cm or more and less than 0.60 kgf / cm ⁇ (Defective): High temperature adhesive strength is 0.55 kgf / Less than cm
• the adhesive sheet was folded and the folded adhesive sheet was punched out with a belt punch having a diameter of 8 mm to prepare an evaluation sample having a thickness of about 1.0 mm and a diameter of 8 mm.
• the evaluation sample was placed on a DHR parallel plate reometer, and the shear strain rate S1 of the evaluation sample at the time when a shear stress of 95 kPa was applied for 5 seconds was measured. Next, the shear strain rate S2 of the evaluation sample was measured 60 seconds after the applied stress was released. ..
• the pressure-sensitive adhesive compositions of Examples 1 to 5 containing a crosslinked isobutene-based polymer having a long-chain alkyl (meth) acrylate polymer chain (component (A)) and a chelate compound of aluminum or zirconium (component (B)) It was excellent in adhesiveness at high temperature (high temperature adhesive strength) and bending resistance (strain recovery rate).
• the pressure-sensitive adhesive composition of Comparative Example 1 containing the component (A') having a butyl methacrylate polymer chain instead of the component (A) was inferior in adhesiveness at high temperature. Further, the pressure-sensitive adhesive composition of Comparative Example 2 containing no component (B) was inferior in bending resistance.
• the pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet of the present invention are useful for manufacturing flexible electronic devices (particularly, manufacturing of laminates constituting flexible devices).

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Epoxy Resins (AREA)
• Adhesives Or Adhesive Processes (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=81973341

Family Applications (1)

Country Status (5)

Citations (6)

Family Cites Families (7)

• 2021
  • 2021-12-09 EP EP21903456.8A patent/EP4261241A4/en active Pending
  • 2021-12-09 WO PCT/JP2021/045244 patent/WO2022124357A1/ja not_active Ceased
  • 2021-12-09 KR KR1020237023144A patent/KR20230117429A/ko active Pending
  • 2021-12-09 JP JP2022568323A patent/JPWO2022124357A1/ja active Pending
  • 2021-12-09 CN CN202180082494.0A patent/CN116601202A/zh active Pending

Patent Citations (6)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events