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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/062—Copolymers with monomers not covered by C09J133/06
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/062—Copolymers with monomers not covered by C09J133/06
  • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/28—Metal sheet
• • 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]
  • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/385—Acrylic polymers
• • G—PHYSICS
  • G06—COMPUTING; CALCULATING OR COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
  • G06F3/0412—Digitisers structurally integrated in a display
• • G—PHYSICS
  • G06—COMPUTING; CALCULATING OR COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
  • G06F3/0416—Control or interface arrangements specially adapted for digitisers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• • 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
  • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

Definitions

• the present invention relates to an adhesive and an adhesive sheet that can be used for bonding optical members constituting a touch panel or the like.
• the touch panel is a laminate of various materials, and an acrylic adhesive is mainly used for bonding. Since the touch panel is installed on the outermost surface of the screen, the pressure-sensitive adhesive for the touch panel is required to have the same heat resistance and wet heat resistance as the liquid crystal display and the plasma display.
• the above problems have been solved by adding an acid component to the adhesive. That is, since the acid component has high water dispersibility, white water is suppressed by widely dispersing water molecules in the layer, and cohesive force is also obtained by hydrogen bonding, so that bubbles in heat-resistant foam are suppressed.
• the capacitive touch panel adhesive is a point where an adhesive layer is directly bonded to a metal surface such as indium tin oxide (ITO). It came to be demanded. Since metal causes corrosion due to the acid component in the pressure-sensitive adhesive and increases the resistance value, a pressure-sensitive adhesive containing no acid component must be used.
• ITO indium tin oxide
• Patent Document 1 a technique for suppressing heat-resistant foaming by using an adhesive whose molecular weight is limited using alkoxyalkyl acrylate has been reported.
• this pressure-sensitive adhesive does not satisfy all the performances of corrosion resistance, wet heat whitening property, and heat resistant foaming property against metals such as ITO, and has poor workability.
• a thick adhesive sheet may be required to increase the distance between members, and it is necessary to form a thick adhesive layer.
• the conventional pressure-sensitive adhesive mainly composed of high molecular weight polymer requires a large amount of solvent to optimize the viscosity at the time of coating. It was difficult to form a thick adhesive layer by coating.
• an object of the present invention is to provide a pressure-sensitive adhesive satisfying all the corrosion resistance, wet heat whitening and heat resistant foaming properties of a metal such as ITO and having good workability.
• the inventors of the present invention have formulated a specific amount of a monomer having a crosslinkable functional group and a hydrogen bonding monomer in an alkoxyalkyl (meth) acrylate,
• the present inventors have found that the above problems can be solved by adjusting the weight average molecular weight to 50,000 or more and less than 400,000 and combining it with an isocyanate-based crosslinking agent, thereby completing the present invention.
• the present invention includes the following components (a1) to (a3), (A1) Alkoxyalkyl (meth) acrylate 20 to 99.8% by mass (A2) Monomer having a crosslinkable functional group 0.1 to 10% by mass (A3) Hydrogen bonding monomer 0.1 to 5% by mass An acrylic polymer having a weight average molecular weight of 50,000 or more and less than 400,000 and substantially free of carboxyl group-containing monomers, (B) A pressure-sensitive adhesive containing an isocyanate-based crosslinking agent.
• the present invention is also a pressure-sensitive adhesive sheet comprising an adhesive layer formed of the above-mentioned pressure-sensitive adhesive on at least one surface of a support.
• the pressure-sensitive adhesive of the present invention contains substantially no acid component and therefore has low metal corrosivity such as ITO, and the molecular weight of the acrylic polymer constituting it is set low, increasing the degree of freedom of the acrylic polymer. This increases the mobility and compatibility of the water molecules that flow into the bed. This makes it possible to suppress the resistance to moist heat whitening, and to quickly dissipate the water molecules that have flowed in, and therefore works more advantageously on the moist heat whitening.
• the pressure-sensitive adhesive of the present invention enables highly non-volatile differentiation without adversely affecting productivity and coating properties, workability is high, particularly when a thick pressure-sensitive adhesive layer is formed. Therefore, the adhesive layer can be formed with a small number of times.
• the pressure-sensitive adhesive of the present invention satisfies all the performances of metal corrosion resistance such as ITO, wet heat whitening and heat-resistant foaming, and has good workability. Suitable for bonding. Moreover, the adhesive sheet using this has the same effect.
• alkoxyalkyl (meth) acrylate of the component (a1) used in the pressure-sensitive adhesive of the present invention examples include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxy Examples thereof include propyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate and the like. Of these, 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate are preferable. By blending this component (a1) in the pressure-sensitive adhesive of the present invention, both step following ability and durability can be achieved.
• Examples of the monomer having a crosslinkable functional group of component (a2) include a monomer having a hydroxyl group. Specific examples include 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth). Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, etc. Can do. Of these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are preferable.
• polymer agglomeration is performed by forming a cross-linked structure by reaction with a cross-linking agent described later and forming a pseudo cross-linked structure by interaction with a hydrogen bonding monomer.
• the force can be improved, and the expansion of bubbles slightly entrained at the time of pasting and foaming due to outgas derived from the material can be suppressed.
• examples of the hydrogen-bonding monomer of component (a3) include a monomer containing a nitrogen atom in the side chain and a lone electron pair on the nitrogen.
• N, N— Amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Amide group-containing monomers such as N-isopropyl (meth) acrylamide, nitrogen-based heterocycle-containing monomers such as (meth) acryloylmorpholine, N-vinylpyrrolidone and vinylpyridine, imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide, ) Cyano group-containing monomers such as acrylonitrile It can gel.
• an amino group-containing (meth) acrylate monomer, an amide group-containing (meth) acrylate monomer, and a nitrogen-based heterocyclic ring-containing monomer are preferable, and acrylamide and diethylaminoethyl acrylate are more preferable.
• this component (a3) into the pressure-sensitive adhesive of the present invention, the water dispersibility in the pressure-sensitive adhesive layer can be increased, the saturated water content can be increased, and the water inflow allowable amount can be increased. For this reason, even after being placed in a moist heat environment, when it is returned to room temperature, the water dissolved in the adhesive layer is stabilized in the adhesive layer, causing water precipitation and whitening due to droplet formation. There is no.
• this hydrogen bondable monomer is a monomer having a crosslinkable functional group or an alkoxylalkyl (metaalkyl group) due to lack of carboxyl groups and low molecular weight.
• acrylate By interacting with acrylate, an effect of forming and supplementing a pseudo cross-linked structure is also obtained. For this reason, it has become possible to achieve both cohesive strength required for heat-resistant foaming property while suppressing wet heat whitening property by making the molecular weight low.
• the acrylic polymer used in the pressure-sensitive adhesive of the present invention comprises 20 to 99.8% by mass (hereinafter simply referred to as “%”) of the above component (a1), preferably 45 to 96.85%, more preferably 50 to 95.3%, component (a2) 0.1-10%, preferably 3-9%, more preferably 4.5-7%, component (a3) 0.1-5%, preferably 0.3. It is obtained by copolymerizing at a ratio of 15 to 4.8%, more preferably 0.2 to 4.5%. Thereby, an acrylic polymer having a weight average molecular weight (Mw) of 50,000 or more and less than 400,000, preferably Mw of 100,000 or more and less than 400,000 can be obtained.
• Mw weight average molecular weight
• a weight average molecular weight means the weight average molecular weight in standard polystyrene conversion measured by the gel permeation chromatography (GPC) as described in an Example.
• the acrylic polymer can be copolymerized with an alkyl (meth) acrylate having a chain alkyl group having 1 to 12 carbon atoms (component (a4)).
• component (a1) It is preferable that the total of component (a4) is 90% or more of the total amount of monomers constituting the acrylic polymer.
• the acrylic polymer may further include an aryl (meth) acrylate such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, or phenyl (meth) acrylate, or an alicyclic ring such as cyclohexyl (meth) acrylate, if necessary.
• Other monomers copolymerizable with the components (a1) to (a4) such as formula (meth) acrylate, vinyl acetate, styrene and the like can also be copolymerized.
• the acrylic polymer can be produced by a known method, but is preferably produced by solution polymerization.
• solution polymerization for example, ethyl acetate, methyl ethyl ketone, toluene, acetone or the like is used as a polymerization solvent.
• a polymerization solvent and a monomer are charged into a reaction vessel, a polymerization initiator is added in an inert gas atmosphere such as nitrogen, and the reaction is carried out at a reaction temperature of about 50 to 90 ° C. for about 4 to 20 hours.
• polymerization initiators used for solution polymerization include azo initiators and peroxide initiators. These polymerization initiators are preferably used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the monomer. Further, an initiator, a chain transfer agent, a monomer, a solvent, and the like may be appropriately added during the polymerization reaction.
• the acrylic polymer obtained above does not substantially contain a carboxyl group-containing monomer.
• substantially free means that the carboxyl group-containing monomer is 0.1% or less, preferably 0.01% or less in the acrylic polymer.
• this acrylic polymer may corrode metals, it is not preferable to contain other acid group-containing monomers such as phosphate groups and sulfonate groups other than carboxyl groups. Therefore, it is preferable that these other acid group-containing monomers are not substantially contained in the acrylic polymer.
• the isocyanate-based crosslinking agent of component (b) used in the pressure-sensitive adhesive of the present invention for example, tolylene diisocyanate, xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, water
• a compound having two isocyanate groups in the molecule such as diphenylmethane diisocyanate added; a compound obtained by adding them to a polyhydric alcohol such as trimethylolpropane or pentaerythritol, an isocyanate compound, an isocyanurate compound, a burette type compound
• known polyether polyols polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene.
• Examples thereof include compounds having two or more isocyanate groups in a urethane prepolymer type molecule that has undergone addition reaction with a polyol, and the like. Specifically, trimethylolpropane adducts of diisocyanate compounds, isocyanurate compounds, etc. Can be mentioned. Among these, tolylene diisocyanate and its derivatives can also be pasted in that the compatibility with the adherend can be improved, the entrainment of bubbles during bonding can be reduced, and the outgassing at high temperatures can be suppressed.
• Hexamethylene diisocyanate and its derivatives are preferred in that they can improve surface followability and improve heat-resistant foaming properties, and further, a trimethylolpropane adduct of tolylene diisocyanate and an isocyanurate compound of hexamethylene diisocyanate. Is preferred.
• this component (b) By adding this component (b) to the pressure-sensitive adhesive of the present invention, the cohesive force of the pressure-sensitive adhesive layer formed can be improved, and the expansion of air bubbles slightly involved during pasting can be suppressed.
• the pressure-sensitive adhesive of the present invention comprises an acrylic polymer obtained by copolymerizing the above-described components (a1) to (a3) (optionally (a4)) and an isocyanate crosslinking agent of component (b) in an arbitrary amount.
• the isocyanate crosslinking agent is added in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the solid content of the acrylic polymer. It is obtained by aging at about 50 ° C. for about 1 to 10 days.
• the pressure-sensitive adhesive of the present invention further contains an antioxidant, a light stabilizer, a tackifier resin, a plasticizer, an antistatic agent, a crosslinking accelerator, a reworking agent, etc., as long as the effects of the present invention are not impaired. You may let them.
• the pressure-sensitive adhesive of the present invention thus obtained can be used for adhesion of various members by coating and drying after being diluted to an appropriate concentration, similarly to known pressure-sensitive adhesives.
• the pressure-sensitive adhesive of the present invention since the pressure-sensitive adhesive of the present invention has a low weight average molecular weight of the acrylic polymer contained in the pressure-sensitive adhesive, the concentration of nonvolatile components can be easily adjusted with various solvents such as vinyl acetate, methyl ethyl ketone, acetone, and toluene. . Therefore, the pressure-sensitive adhesive of the present invention can easily make the thickness of the pressure-sensitive adhesive after coating a desired thickness.
• the pressure-sensitive adhesive of the present invention can have a high non-volatile differentiation, for example, a non-volatile component (value obtained by the measurement method described in Examples) of 10 to 70%, preferably 30 to 60%. Can be formed with a small number of times.
• a non-volatile component value obtained by the measurement method described in Examples
• the leveling property of the coating film after coating and drying is improved, and further, the drying time is shortened and the workability is improved.
• the amount of the volatile solvent is small, the burden on the environment can be reduced.
• the pressure-sensitive adhesive of the present invention satisfies all the metal corrosion resistance, wet whitening and heat-resistant foaming properties, particularly ITO, and has good workability for thick film coating.
• the optical member has a metal surface, and more preferably, the optical member can be used for bonding the metal surface.
• the optical member bonded with the adhesive of the present invention is an antireflection film made of glass, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, triacetyl cellulose, polysulfone, polyarylate, etc. constituting a touch panel, a polarizing plate, a retardation plate , Light guide plate, wave plate, optical compensation film, brightness enhancement film, reflection film, transparent conductive film, design film, prism sheet, color filter, etc., and the metal surface is indium tin oxide layer, copper foil, silver wiring, etc. It is.
• the pressure-sensitive adhesive of the present invention can be a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive is provided on at least one surface of a support.
• a support body As a support body, the above-mentioned various optical members, the polyethylene terephthalate film by which the peeling process was carried out, an ITO vapor deposition film, etc. are mentioned, for example.
• Such an adhesive sheet is preferable for attaching optical members constituting the touch panel.
• the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is 25 to 500 ⁇ m, preferably 20 to 400 ⁇ m. Particularly, those having a thickness of 100 to 300 ⁇ m can be preferably used for bonding metal surfaces of optical members constituting a touch panel that requires a sufficient space between members.
• Example 1 Manufacture of adhesive sheet: In a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen introduction tube, 60 parts by mass of methoxyethyl acrylate (MEA), 31 parts by mass of butyl acrylate (BA), 2-hydroxyethyl acrylate (HEA) 5 1 part by mass, 2 parts by mass of acrylamide (AM) and 100 parts by mass of methyl ethyl ketone (MEK) are added, 0.1 part by mass of 2,2′-azobisisobutyronitrile is added, and the air in the reaction vessel is replaced with nitrogen gas. did. Next, the mixture was heated to 70 ° C. with stirring in a nitrogen atmosphere, and then reacted for 5 hours. After completion of the reaction, the solution was diluted with methyl ethyl ketone to a nonvolatile content concentration of 40% by mass to obtain a (meth) acrylic polymer solution.
• MEA methoxyethyl acrylate
• BA buty
• Isocyanate-based crosslinking agent (TD-75: trimethylolpropane adduct of tolylene diisocyanate: manufactured by Soken Chemical Co., Ltd.) with respect to 100 parts by mass of the solid content of the (meth) acrylic polymer solution obtained above. 4 mass parts was added and the adhesive was obtained.
• This pressure-sensitive adhesive was coated on a polyethylene terephthalate substrate so that the thickness after drying was 175 ⁇ m, and dried for 2 minutes with a dryer at 80 ° C. to remove the solvent. Next, a peeled polyethylene terephthalate film was bonded to the pressure-sensitive adhesive layer surface, and aged for 7 days at 23 ° C. and 65% RH to obtain a pressure-sensitive adhesive sheet.
• Example 2 Manufacture of adhesive sheet: A pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 7 parts by mass and AM was changed to 2 parts by mass of diethylaminoethyl acrylate (DMAEA).
• HEA was changed to 7 parts by mass
• AM was changed to 2 parts by mass of diethylaminoethyl acrylate (DMAEA).
• Example 3 Manufacture of adhesive sheet: In Example 1, a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that MEA was changed to 25 parts by mass, HEA was changed to 7 parts by mass, and BA was changed to 61 parts by mass.
• Example 4 Manufacture of adhesive sheet: In Example 1, an adhesive and an adhesive sheet were produced in the same manner as in Example 1 except that MEA was changed to 90 parts by mass and BA was changed to 1 part by mass.
• Example 5 Manufacture of adhesive sheet: A pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 5 parts by mass and BA was changed to 33 parts by mass.
• Example 6 Manufacture of adhesive sheet: In Example 1, a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 9 parts by mass and BA was changed to 29 parts by mass.
• Example 7 Manufacture of adhesive sheet: In Example 1, a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that AM was changed to 0.2 parts by mass and BA was changed to 32.8 parts by mass.
• Example 8 Manufacture of adhesive sheet: In Example 1, a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as Example 1 except that AM was changed to 4.5 parts by mass and BA was changed to 28.5 parts by mass.
• Example 9 Manufacture of adhesive sheet: In Example 1, HEA was changed to 9 parts by mass, BA was changed to 29 parts by mass, and N-dodecyl mercaptan as a chain transfer agent was added to react with 0.005 parts by mass. A pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that the amount was adjusted to 50%.
• Example 10 Manufacture of adhesive sheet: In Example 1, a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 9 parts by mass, BA was changed to 29 parts by mass, and MEK was changed to 95 parts by mass.
• Example 11 Manufacture of adhesive sheet: In Example 1, an adhesive and an adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 4 parts by mass and BA was changed to 34 parts by mass.
• Example 12 Manufacture of adhesive sheet: A pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 0.5 parts by mass and BA was changed to 37.5 parts by mass.
• Example 13 Manufacture of adhesive sheet: In Example 1, a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 1 part by mass and BA was changed to 37 parts by mass.
• Example 14 Manufacture of adhesive sheet: In Example 1, a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 2 parts by mass and BA was changed to 36 parts by mass.
• Example 15 Manufacture of adhesive sheet: A pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 7 parts by mass and AM was changed to 2 parts by mass of n-vinylpyrrolidone (n-VP).
• Example 16 Manufacture of adhesive sheet: A pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 7 parts by mass and AM was changed to acryloylmorpholine (ACMO).
• Example 17 Manufacture of adhesive sheet:
• Example 1 is the same as Example 1 except that HEA is changed to 7 parts by mass and TD-75 is changed to 0.5 parts by mass of TPA-100 (isocyanurate of hexamethylene diisocyanate: manufactured by Asahi Kasei Co., Ltd.). Similarly, an adhesive and an adhesive sheet were produced.
• TPA-100 isocyanurate of hexamethylene diisocyanate: manufactured by Asahi Kasei Co., Ltd.
• Example 18 Manufacture of adhesive sheet: In Example 1, the pressure-sensitive adhesive and pressure-sensitive adhesive sheet were the same as Example 1 except that BA was changed to 33 parts by mass and TD-75 was changed to 0.5 part by mass of TPA-100 (manufactured by Asahi Kasei Corporation). Manufactured.
• Example 19 Manufacture of adhesive sheet: Example 1 Example 1 except that MEA was changed to 90 parts by mass, BA was changed to 1 part by mass, and TD-75 was changed to 0.5 parts by mass of TPA-100 (manufactured by Asahi Kasei Corporation). A pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as described above.
• Example 1 Manufacture of adhesive sheet: In Example 1, an adhesive and an adhesive sheet were produced in the same manner as in Example 1 except that MEA was changed to 10 parts by mass, HEA was changed to 7 parts by mass, and BA was changed to 81 parts by mass.
• Example 1 a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 0 parts by mass and BA was changed to 38 parts by mass.
• Example 1 a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 12 parts by mass and BA was changed to 26 parts by mass.
• Example 4 Manufacture of adhesive sheet: In Example 1, HEA was changed to 7 parts by mass, AM was changed to 0 parts by mass, BA was changed to 33 parts by mass, and the resulting (meth) acrylic polymer solution was further a crosslinking accelerator. A pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that 0.1 part by mass of EDP-300 (manufactured by ADEKA Corporation) was added.
• Comparative Example 5 Manufacture of adhesive sheet: A pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 7 parts by mass, AM was changed to 7 parts by mass, and BA was changed to 26 parts by mass.
• Example 1 the pressure-sensitive adhesive and the pressure-sensitive adhesive sheet were the same as Example 1 except that HEA was changed to 7 parts by mass, BA was changed to 30 parts by mass, and 1 part by mass of acrylic acid (AA) was added to BA. Manufactured.
• Example 7 Manufacture of adhesive sheet:
• a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that HEA was changed to 7 parts by mass and N-dodecyl mercaptan as a chain transfer agent was added in an amount of 0.01 part by mass.
• Example 8 Manufacture of adhesive sheet: In Example 1, except that HEA was changed to 7 parts by mass and MEK was changed to 80 parts by mass, the same procedure as in Example 1 was carried out, and the non-volatile content concentration was adjusted to 30% after the reaction was completed. Manufactured.
• Example 10 Manufacture of adhesive sheet: In Example 1, HEA was changed to 1 part by mass of 4-hydroxybutyl acrylate (4HBA), AM was changed to 0 part by mass, BA was changed to 39 parts by mass, and the nonvolatile content concentration was changed to 30% after completion of the reaction.
• a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that 0.1 weight of EDP-300 (manufactured by Asahi Denka Co., Ltd.) as a crosslinking accelerator was added.
• Test example 1 Measurement of physical properties of adhesives and adhesive sheets: The weight average molecular weights of the pressure-sensitive adhesives obtained in Examples 1 to 19 and Comparative Examples 1 to 10 were measured by the following measuring method, and the degree of dispersion was calculated by the following method. Moreover, the wet heat whitening property, heat-resistant foaming property, ITO corrosivity, coating property, and workability
• Nonvolatile content 100 ⁇ [weight after heating (n3-n1) / weight before heating (n2-n1)]
• a pressure-sensitive adhesive sheet cut to 50 mm ⁇ 60 mm was attached to a polycarbonate plate wiped with isopropyl alcohol, and autoclaved at 50 ° C. ⁇ 5 atm for 20 minutes. Then, after standing at room temperature for 1 hour, (1) placed in an 80 ° C. environment for 500 hours, or (2) placed in an 80 ° C., 90% environment for 500 hours, and left at 23 ° C., 65% RH for 1 hour. After placing, the foaming of the pressure-sensitive adhesive layer was visually confirmed.
• the criteria for evaluation are as follows.
• Mw 50,000 or more and less than 400,000 obtained by copolymerizing alkoxyalkyl (meth) acrylate (a1), monomer (a2) having a crosslinkable functional group, and hydrogen bonding monomer (a3) at a specific ratio.
• the acrylic polymer substantially free of the carboxyl group-containing monomer and the pressure-sensitive adhesive containing the isocyanate-based crosslinking agent (b) are resistant to heat and heat whitening, heat-resistant foaming, and without corroding the ITO electrode. The workability of coating was also excellent.
• Comparative Example 1 having a small copolymerization amount of alkoxyalkyl (meth) acrylate (a1) is inferior in moisture and heat whitening resistance, and the copolymerization amount of monomer (a2) having a crosslinkable functional group deviates from the scope of the present application.
• the heat-resistant foamability is inferior.
• Comparative Examples 4 and 5 in which the copolymerization amount of the hydrogen bonding monomer (a3) deviates from the scope of the present application the heat-resistant foaming property is insufficient in the molecular weight range of the present application, does not contain the hydrogen bonding monomer (b), and has a molecular weight.
• Comparative Example 10 exceeding the scope of the present application, the heat-resistant foaming property is similarly inferior, and further, the water dispersibility is inferior due to the high molecular weight, so the heat-and-moisture whitening resistance is not sufficient, and the workability of thick film coating is also low. Is also inferior. Further, in Comparative Examples 7 and 8 deviating from the molecular weight range of the present application, Comparative Example 7 having a low molecular weight has insufficient heat-resistant foaming property, and Comparative Example 8 having a high molecular weight has poor workability for thick film coating. Yes.
• Comparative Example 7 having a carboxyl group in the acrylic polymer, the ITO was corroded, and a metal crosslinking agent (M-5AT) was added in place of the isocyanate crosslinking agent (TD-75). In Comparative Example 9, the heat resistance foaming property is inferior.
• M-5AT metal crosslinking agent
• the pressure-sensitive adhesive and pressure-sensitive adhesive sheet of the present invention can be used for bonding optical members constituting touch panels and the like.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Engineering & Computer Science (AREA)
• Theoretical Computer Science (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Human Computer Interaction (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesive Tapes (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Liquid Crystal (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=46457466

Family Applications (1)

Country Status (5)

Cited By (12)

Families Citing this family (12)

Citations (6)

Family Cites Families (3)

• 2011
  • 2011-12-26 KR KR1020137016347A patent/KR101840707B1/ko active IP Right Grant
  • 2011-12-26 JP JP2012551836A patent/JP5712229B2/ja active Active
  • 2011-12-26 WO PCT/JP2011/079997 patent/WO2012093607A1/ja active Application Filing
  • 2011-12-26 CN CN201180064049.8A patent/CN103314068B/zh active Active
• 2012
  • 2012-01-04 TW TW101100301A patent/TWI529229B/zh active

Patent Citations (6)

Also Published As

Similar Documents

Legal Events