WO2018030434A1 - 接着剤組成物、硬化体、電子部品及び組立部品 - Google Patents

接着剤組成物、硬化体、電子部品及び組立部品 Download PDF

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WO2018030434A1
WO2018030434A1 PCT/JP2017/028836 JP2017028836W WO2018030434A1 WO 2018030434 A1 WO2018030434 A1 WO 2018030434A1 JP 2017028836 W JP2017028836 W JP 2017028836W WO 2018030434 A1 WO2018030434 A1 WO 2018030434A1
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adhesive composition
meth
acrylate
group
preferable
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PCT/JP2017/028836
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English (en)
French (fr)
Japanese (ja)
Inventor
智一 玉川
拓身 木田
彰 結城
高橋　徹
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積水化学工業株式会社
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Priority to CN201780008422.5A priority Critical patent/CN108603091B/zh
Priority to KR1020187021253A priority patent/KR102326096B1/ko
Priority to JP2017546263A priority patent/JP6878289B2/ja
Publication of WO2018030434A1 publication Critical patent/WO2018030434A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to an adhesive composition that is excellent in adhesiveness and easy to rework at a low temperature.
  • the present invention also relates to a cured product of the adhesive composition, and an electronic component and an assembly component having the cured product of the adhesive composition.
  • liquid crystal display elements In recent years, liquid crystal display elements, organic EL display elements, and the like are widely used as display elements having features such as thinness, light weight, and low power consumption.
  • a photocurable resin composition is usually used for sealing a liquid crystal or a light emitting layer, adhering various members such as a substrate, an optical film, and a protective film.
  • a frame is being made (hereinafter also referred to as a narrow frame design).
  • the photocurable resin composition may be applied to a portion where light does not reach sufficiently.
  • the photocurable resin composition applied to a portion where light does not reach Had the problem of insufficient curing.
  • This problem is particularly remarkable in a display element with a narrow frame design. Therefore, a photothermosetting resin composition is used as a resin composition that can be sufficiently cured even when applied to a portion where light does not reach, and photocuring and thermosetting are also used in combination. There was a possibility of adversely affecting the elements and the like by heating.
  • Patent Document 1 discloses a thermosetting adhesive containing an epoxy compound having a number average molecular weight of 600 to 1,000.
  • the thermosetting adhesive as disclosed in Patent Document 1 is not suitable for bonding electronic components that may be damaged by heat.
  • Patent Document 2 discloses a moisture curable resin composition that is crosslinked and cured by reacting an isocyanate group in a resin with moisture (moisture) in air or an adherend.
  • the thermosetting adhesive as disclosed in Patent Document 1 is not suitable for bonding electronic components that may be damaged by heat.
  • thermosetting adhesives tend to have poor adhesive properties when a large load is applied for a long time, making it difficult to obtain highly reliable adhesives, especially for display elements with narrow frame designs. there were.
  • JP 2000-178342 A Japanese Patent Laid-Open No. 2002-212534
  • the present inventors have come up with the idea of a new type of moisture curable resin composition imparted with reworkability.
  • the moisture curable resin composition as described above has adhesiveness and reworkability (removability). ) Is difficult to achieve.
  • reworking is performed under high temperature conditions, there is a problem of damaging electronic components, etc., so that it does not require heating at high temperatures when fixed, and has excellent adhesiveness.
  • An object of this invention is to provide the adhesive composition which is excellent in adhesiveness and is easy to rework at low temperature.
  • Another object of the present invention is to provide a cured product of the adhesive composition, and an electronic component and an assembly component having the cured product of the adhesive composition.
  • the present invention is an adhesive composition containing a moisture curable resin and a foaming agent.
  • the present invention is described in detail below.
  • the present inventors have found that an adhesive composition that is excellent in adhesiveness and easy to rework at low temperature can be obtained by blending a foaming agent with a moisture curable resin composition. It came to complete.
  • the adhesive composition of the present invention has a strong adhesive force after use as an adhesive, but can be peeled off by heating at a relatively low temperature during rework, so-called thermal peeling. This is a mold adhesive composition.
  • the adhesive composition of the present invention contains a foaming agent.
  • the adhesive composition of this invention becomes excellent in the rework property in low temperature.
  • the “foaming agent” include inorganic foaming agents, organic foaming agents, and thermally expandable particles.
  • the shape of the said foaming agent is not specifically limited, It is preferable that it is a particle shape.
  • the “inorganic foaming agent” and the “organic foaming agent” mean those that generate gas by an action such as decomposition by heating.
  • thermally expandable particles include a low-boiling compound as a core agent in a shell made of a thermoplastic resin, and the core agent volatilizes by heating to increase the gas pressure in the shell, thereby forming the shell. It means particles whose volume is increased by softening the thermoplastic resin.
  • the inorganic foaming agent examples include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, etc., polyphosphate amide, ammonium polyphosphate, melamine phosphate, etc., light metals such as magnesium powder and aluminum powder, hydrogen Examples thereof include hydrides such as sodium borohydride and sodium hydride, and azides such as sodium azide.
  • organic foaming agent examples include azo compounds such as azodicarbonamide and azobisisobutyronitrile, N, N′-dinitrosopentamethylenetetramine, N, N′-dinitroso-N, N′-dimethylterephthalate.
  • Nitroso compounds such as amides, hydrazide compounds such as p-toluenesulfonyl hydrazide, p, p′-oxybis (benzenesulfonylhydrazide), hydrazolcarbonamide, p-toluenesulfonyl azide, acetone-p-sulfonylhydrazone, melamine, Urea, dicyandiamide, starch, cellulose, saccharides, dipentaerythritol and the like can be mentioned.
  • hydrazide compounds such as p-toluenesulfonyl hydrazide, p, p′-oxybis (benzenesulfonylhydrazide), hydrazolcarbonamide, p-toluenesulfonyl azide, acetone-p-sulfonylhydrazone, melamine, Urea, dicyandiamide, starch,
  • thermoplastic resin constituting the shell of the thermally expandable particles examples include polyolefins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymers, polyvinyl chloride, polystyrene, ethylene-methyl methacrylate copolymers, Examples thereof include vinylidene chloride, polymethyl methacrylate, methyl methacrylate-acrylonitrile copolymer, vinylidene chloride-acrylonitrile copolymer, polyacrylonitrile and the like. Of these, vinylidene chloride-acrylonitrile copolymer and methyl methacrylate-acrylonitrile copolymer are preferable.
  • part or all of the surface of the shell may be covered with a material other than the thermoplastic resin.
  • coating modes include thin film coating with inorganic materials and / or organic materials, and surface coating with fine particles.
  • Examples of the thin film coating with the inorganic material and / or organic material include surface coating by electrolytic plating or electroless plating, surface coating with a silane coupling agent, and the like.
  • Examples of the plating material used for the electrolytic plating or the electroless plating include metal materials such as copper, aluminum, gold, silver, nickel, lead, and solder. Of these, copper and nickel are preferable from the viewpoint of cost.
  • the plating layer formed by the electrolytic plating or the electroless plating may be a single layer or a multilayer.
  • the preferable lower limit of the thickness of the coating layer formed by thin film coating with the inorganic material and / or organic material is 10 nm, and the preferable upper limit is 10 ⁇ m.
  • the range of the thickness of the coating layer is within this range, the softening of the shell due to moisture can be sufficiently suppressed, and the foaming of the thermally expandable particles can be appropriately controlled.
  • the minimum with more preferable thickness of the said coating layer is 100 nm, and a more preferable upper limit is 4 micrometers.
  • a preferable lower limit of the coverage of the coating layer is 30%.
  • the coverage of the coating layer is 30% or more, the softening of the shell due to moisture can be sufficiently suppressed, and the foaming of the thermally expandable particles can be appropriately controlled.
  • a more preferable lower limit of the coverage of the coating layer is 60%.
  • the practical upper limit of the coverage of the coating layer is 100%.
  • examples of the fine particles include silica, alumina, zirconia, and magnesia. Of these, silica and alumina are preferable from the viewpoint of cost.
  • the preferable lower limit of the average particle diameter of the fine particles is 10 nm, and the preferable upper limit is 1 ⁇ m.
  • the average particle diameter of the fine particles is within this range, the softening of the shell due to moisture can be sufficiently suppressed, and the foaming of the thermally expandable particles can be appropriately controlled.
  • a more preferable lower limit of the average particle diameter of the fine particles is 20 nm, and a more preferable upper limit is 500 nm.
  • the average particle diameter of the fine particles can be measured by a laser diffraction scattering method.
  • the laser diffraction scattering method for example, Mastersizer Hydro 2000SM (manufactured by Malvern) or the like can be used.
  • a preferable lower limit of the coverage of the fine particles is 30%.
  • the coverage of the fine particles is 30% or more, the softening of the shell due to moisture can be sufficiently suppressed, and the foaming of the thermally expandable particles can be appropriately controlled.
  • a more preferable lower limit of the coverage of the fine particles is 60%.
  • the practical upper limit of the fine particle coverage is 100%.
  • Examples of the low boiling point compound that is the core agent of the thermally expandable particles include ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, n-heptane, isooctane, and cyclohexane.
  • Examples thereof include low molecular weight hydrocarbons, tetraalkylsilanes such as tetramethylsilane and trimethylethylsilane, and azodicarbonamide. Of these, simple substances or mixtures of isobutane, isopentane, isooctane and the like are preferable.
  • grain is 5 weight%, and a preferable upper limit is 50 weight%.
  • the content of the low boiling point compound is 5% by weight or more, the obtained heat-expandable particles are more excellent in foaming performance.
  • the content of the low boiling point compound is 50% by weight or less, the obtained heat-expandable particles are more excellent in the strength of the shell and can be foamed at a higher expansion ratio.
  • a more preferable lower limit of the content of the low boiling point compound in the thermally expandable particles is 10% by weight, and a more preferable upper limit is 30% by weight.
  • heat-expandable particles examples include 031-DU-40, 031-WUF-40, 051-DU-40, 551-DU-40, 053-DU-40, and 053-WU. -40,007-WUF-40, 461-DU-40, 461-DU-20 (all manufactured by Akzo Nobel), F-30, F-36, F-36LV, F-48, FN-80GS, F -50, F-65 (both manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) and the like.
  • the minimum with a preferable foaming start temperature is 60 degreeC, and a preferable upper limit is 130 degreeC.
  • the foaming start temperature of the foaming agent is 60 ° C. or higher, the resulting adhesive composition is more excellent in adhesiveness.
  • the foaming start temperature of the foaming agent is 130 ° C. or lower, the resulting adhesive composition is more excellent in reworkability at low temperatures.
  • the minimum with more preferable foaming start temperature of the said foaming agent is 70 degreeC, a more preferable upper limit is 110 degreeC, and a still more preferable upper limit is 100 degreeC.
  • the foaming start temperature of the said foaming agent means the temperature when the displacement of a height direction turns to positive when the said foaming agent is heated with a thermomechanical analyzer (TMA).
  • the minimum with the preferable average particle diameter of the said foaming agent is 5 micrometers, and a preferable upper limit is 20 micrometers.
  • the average particle size of the foaming agent is 5 ⁇ m or more, the foaming efficiency of the foaming agent in the obtained adhesive composition is high, and thus the peelability of the adhesive composition is excellent.
  • the average particle size of the foaming agent is 20 ⁇ m or less, the adhesive strength of the resulting adhesive composition is excellent.
  • the upper limit with a more preferable average particle diameter of the said foaming agent is 18 micrometers. The effect of the average particle diameter is remarkably confirmed when the foaming agent is a thermally expandable particle.
  • the average particle diameter of the said foaming agent can be measured by the laser diffraction scattering method.
  • the laser diffraction scattering method for example, Mastersizer Hydro 2000SM (manufactured by Malvern) or the like can be used.
  • the preferable lower limit of the content of the foaming agent in 100 parts by weight of the adhesive composition of the present invention is 1 part by weight, and the preferable upper limit is 50 parts by weight.
  • the content of the foaming agent is within this range, the resulting adhesive composition is more excellent in the effect of achieving both adhesiveness and reworkability.
  • the minimum with more preferable content of the said foaming agent is 5 weight part, A more preferable upper limit is 40 weight part, Furthermore, a preferable upper limit is 20 weight part.
  • the adhesive composition of the present invention contains a moisture curable resin.
  • the moisture curable resin include a moisture curable urethane resin and a hydrolyzable silyl group-containing resin. Of these, moisture-curable urethane resins are preferable.
  • the moisture curable urethane resin has a urethane bond and an isocyanate group, and the isocyanate group in the molecule is cured by reacting with moisture in the air or the adherend.
  • the moisture curable urethane resin may have only one isocyanate group in one molecule, or may have two or more. Especially, it is preferable to have an isocyanate group at both ends of the main chain of the molecule.
  • the moisture curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.
  • polyol compound used as a raw material for the moisture curable urethane resin As a polyol compound used as a raw material for the moisture curable urethane resin, a known polyol compound usually used in the production of polyurethane can be used. For example, polyester polyol, polyether polyol, polyalkylene polyol, polycarbonate polyol Etc. These polyol compounds may be used independently and may be used in combination of 2 or more type.
  • polyester polyol examples include a polyester polyol obtained by reaction of a polyvalent carboxylic acid and a polyol, and a poly- ⁇ -caprolactone polyol obtained by ring-opening polymerization of ⁇ -caprolactone.
  • polyvalent carboxylic acid used as a raw material for the polyester polyol examples include terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberin.
  • examples include acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, dodecamethylene dicarboxylic acid and the like.
  • polyester polyol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1,6-hexane.
  • Diol, diethylene glycol, cyclohexanediol, etc. are mentioned.
  • polyether polyol examples include ethylene glycol, propylene glycol, ring-opening polymer of tetrahydrofuran, ring-opening polymer of 3-methyltetrahydrofuran, and random copolymers or block copolymers of these or derivatives thereof, bisphenol Type polyoxyalkylene modified products.
  • the modified bisphenol-type polyoxyalkylene is a polyether polyol obtained by addition reaction of alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen portion of the bisphenol-type molecular skeleton, A random copolymer or a block copolymer may be used.
  • the modified bisphenol-type polyoxyalkylene preferably has one or more alkylene oxides added to both ends of the bisphenol-type molecular skeleton. It does not specifically limit as a bisphenol type, A type, F type, S type etc. are mentioned, Preferably it is bisphenol A type.
  • polyalkylene polyol examples include polybutadiene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.
  • polycarbonate polyol examples include polyhexamethylene carbonate polyol and polycyclohexane dimethylene carbonate polyol.
  • an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound are preferably used.
  • the aromatic polyisocyanate compound include diphenylmethane diisocyanate, a liquid modified product of diphenylmethane diisocyanate, polymeric MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate, and the like.
  • Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and cyclohexane.
  • Examples include diisocyanate, bis (isocyanatemethyl) cyclohexane, dicyclohexylmethane diisocyanate, and the like.
  • diphenylmethane diisocyanate and modified products thereof are preferable from the viewpoint of low vapor pressure, low toxicity, and ease of handling.
  • the said polyisocyanate compound may be used independently and may be used in combination of 2 or more type.
  • the said moisture hardening type urethane resin is obtained using the polyol compound which has a structure represented by following formula (1).
  • a polyol compound having a structure represented by the following formula (1) it is possible to obtain a composition excellent in adhesiveness and a cured product that is flexible and has good elongation, and is compatible with the radical polymerizable compound. It will be excellent.
  • a polyether polyol composed of a ring-opening polymerization compound of propylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group are preferable.
  • R represents a hydrogen atom, a methyl group, or an ethyl group
  • l is an integer of 0 to 5
  • m is an integer of 1 to 500
  • n is an integer of 1 to 10.
  • l is preferably from 0 to 4
  • m is preferably from 50 to 200
  • n is preferably from 1 to 5.
  • the case where l is 0 means that the carbon bonded to R is directly bonded to oxygen.
  • the hydrolyzable silyl group in the molecule is cured by reacting with moisture in the air or in the adherend.
  • the hydrolyzable silyl group-containing resin may have only one hydrolyzable silyl group in one molecule, or may have two or more. Especially, it is preferable to have a hydrolyzable silyl group at both ends of the main chain of the molecule.
  • the hydrolyzable silyl group is represented by the following formula (2).
  • each R 1 independently represents an optionally substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or , —OSiR 2 3 (wherein R 2 is each independently a hydrocarbon group having 1 to 20 carbon atoms).
  • X is a hydroxyl group or a hydrolysable group each independently.
  • a is an integer of 1 to 3.
  • the hydrolyzable group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, A mercapto group etc. are mentioned.
  • a halogen atom, an alkoxy group, an alkenyloxy group and an acyloxy group are preferable because of high activity, and an alkoxy group such as a methoxy group and an ethoxy group is more preferable because of its mild hydrolyzability and easy handling.
  • An ethoxy group is more preferable. From the viewpoint of safety, an ethoxy group and an isopropenoxy group, in which the compounds eliminated by the reaction are ethanol and acetone, respectively, are preferable.
  • the hydroxy group or the hydrolyzable group can be bonded in the range of 1 to 3 to one silicon atom. When two or more of the hydroxy groups or the hydrolyzable groups are bonded to one silicon atom, these groups may be the same or different.
  • a in formula (2) is preferably 2 or 3, and particularly preferably 3, from the viewpoint of curability. From the viewpoint of storage stability, a is preferably 2.
  • R 1 in the above formula (2) is, for example, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, or a trimethylsiloxy group. Chloromethyl group, methoxymethyl group and the like. Of these, a methyl group is preferable.
  • hydrolyzable silyl group examples include methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, tris (2-propenyloxy) silyl group, triacetoxysilyl group, (chloromethyl) dimethoxysilyl group, ( (Chloromethyl) diethoxysilyl group, (dichloromethyl) dimethoxysilyl group, (1-chloroethyl) dimethoxysilyl group, (1-chloropropyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group Group, (ethoxymethyl) dimethoxysilyl group, (1-methoxyethyl) dimethoxysilyl group, (aminomethyl) dimethoxysilyl group, (N, N-dimethylaminomethyl) dimethoxysilyl group, (N, N-die
  • hydrolyzable silyl group-containing resin examples include a hydrolyzable silyl group-containing (meth) acrylic resin, a molecular chain terminal or an organic polymer having a hydrolyzable silyl group at the molecular chain terminal site, and a hydrolyzable silyl group. Containing polyurethane resin and the like.
  • the hydrolyzable silyl group-containing (meth) acrylic resin preferably has a repeating structural unit derived from hydrolyzable silyl group-containing (meth) acrylic acid ester and (meth) acrylic acid alkyl ester in the main chain.
  • hydrolyzable silyl group-containing (meth) acrylic acid ester examples include 3- (trimethoxysilyl) propyl (meth) acrylate, 3- (triethoxysilyl) propyl (meth) acrylate, and (meth) acrylic.
  • examples thereof include ethyl, trimethoxysilylmethyl (meth) acrylate, triethoxysilylmethyl (meth) acrylate, methyl (meth) acrylate (methyldimethoxysilyl), and the like.
  • Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate.
  • hydrolyzable silyl group-containing (meth) acrylic resin specifically, for example, a hydrolyzable silicon group-containing (meth) acrylic acid ester system described in International Publication No. 2016/035718 Examples include a polymer synthesis method.
  • the organic polymer having a hydrolyzable silyl group at the end of the molecular chain or at the end of the molecular chain has a hydrolyzable silyl group at at least one of the main chain end and the side chain end.
  • the backbone structure of the main chain is not particularly limited, and examples thereof include saturated hydrocarbon polymers, polyoxyalkylene polymers, (meth) acrylic acid ester polymers, and the like.
  • polyoxyalkylene polymer examples include polyoxyethylene structure, polyoxypropylene structure, polyoxybutylene structure, polyoxytetramethylene structure, polyoxyethylene-polyoxypropylene copolymer structure, polyoxypropylene-poly Examples include polymers having an oxybutylene copolymer structure.
  • Examples thereof include a method for synthesizing an organic polymer having a crosslinkable silyl group only at a molecular chain terminal site.
  • a reactive silicon group-containing compound described in International Publication No. 2012/117902 examples include a method for synthesizing a polyoxyalkylene polymer.
  • hydrolyzable silyl group-containing polyurethane resin for example, when a polyurethane resin is produced by reacting a polyol compound and a polyisocyanate compound, a silyl group-containing compound such as a silane coupling agent is further added.
  • a silyl group-containing compound such as a silane coupling agent
  • the method of making it react is mentioned. Specific examples include a method for synthesizing a urethane oligomer having a hydrolyzable silyl group described in JP-A-2017-48345.
  • silane coupling agent examples include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxy-ethoxy) silane, ⁇ - (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, and ⁇ -glycidoxy.
  • silane coupling agents may be used alone or in combination of two or more.
  • the moisture curable resin may have a radical polymerizable functional group.
  • the radical polymerizable functional group that the moisture curable resin may have is preferably a group having an unsaturated double bond, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
  • the moisture curable resin having a radical polymerizable functional group is not included in the radical polymerizable compound described later, and is treated as a moisture curable resin.
  • the weight average molecular weight of the moisture curable resin is not particularly limited, but a preferable lower limit is 800 and a preferable upper limit is 10,000. When the weight-average molecular weight of the moisture curable resin is within this range, the resulting adhesive composition has excellent flexibility without excessively high crosslinking density upon curing, and also has excellent coating properties. .
  • the more preferable lower limit of the weight average molecular weight of the moisture curable resin is 2000, the more preferable upper limit is 8000, the still more preferable lower limit is 2500, and the further preferable upper limit is 6000.
  • the said weight average molecular weight is a value calculated
  • Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK). Moreover, tetrahydrofuran etc. are mentioned as a solvent used by GPC.
  • the preferable lower limit of the content of the moisture curable resin in 100 parts by weight of the adhesive composition of the present invention is 20 parts by weight, and the preferable upper limit is 90 parts by weight.
  • the content of the moisture curable resin is within this range, the resulting adhesive composition is more excellent in moisture curability while maintaining excellent weather resistance and flexibility of the cured product.
  • the minimum with more preferable content of the said moisture curable resin is 30 weight part, and a more preferable upper limit is 70 weight part.
  • FIG. 1 is a schematic view showing the adhesion state of an adherend by the adhesive composition of the present invention when (a) the thickness of the adhesive layer is small and (b) large. As shown in FIG. 1, the greater the thickness 3 of the adhesive layer made of the adhesive composition 2 that adheres the adherend 1, the greater the amount of the foaming agent 5 present in the adhesive composition 2 per unit area 4. Become more.
  • the adhesive composition of the present invention preferably contains a radical polymerizable compound and a photo radical polymerization initiator. That is, by containing the radically polymerizable compound and the photoradical polymerization initiator, photocurability and moisture curability are ensured, and both cohesion and reworkability are more effective.
  • a radical polymerizable compound and a photo radical polymerization initiator that is, by containing the radically polymerizable compound and the photoradical polymerization initiator, photocurability and moisture curability are ensured, and both cohesion and reworkability are more effective.
  • Such an adhesive composition of the present invention can be suitably used especially for an adhesive used for a sealant for a display element or a case connection of a narrow frame design.
  • the radical polymerizable compound is not particularly limited as long as it is a radical polymerizable compound having photopolymerizability and is a compound having a radical polymerizable functional group in the molecule.
  • a compound having an unsaturated double bond as a radical polymerizable functional group is suitable, and a compound having a (meth) acryloyl group (hereinafter also referred to as “(meth) acrylic compound”) is particularly preferable from the viewpoint of reactivity. Is preferred.
  • the “(meth) acryloyl” means acryloyl or methacryloyl
  • the “(meth) acryl” means acryl or methacryl.
  • the (meth) acrylic compound examples include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like.
  • the “(meth) acrylate” means acrylate or methacrylate.
  • the said urethane (meth) acrylate does not have a residual isocyanate group.
  • Examples of monofunctional compounds among the (meth) acrylic acid ester compounds include phthalimide acrylates such as N-acryloyloxyethyl hexahydrophthalimide, various imide (meth) acrylates, methyl (meth) acrylate, and ethyl (meth).
  • Examples of the bifunctional compound among the (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
  • those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri ( (Meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, Tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra Meth) acrylate, dipentaerythritol pen
  • Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
  • Examples of the epoxy compound as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl bisphenol A type epoxy resin. , Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Ren phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins.
  • Examples of commercially available epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRY370R ), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, Epoxy ester 200PA, Epoxy ester 80MF Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-3
  • the urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.
  • isocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diene Isocyanate, 1,6,11-undecane triisocyanate and the like.
  • MDI diphenylmethane-4,4′-diisocyanate
  • XDI
  • isocyanate compound a chain-extended isocyanate compound obtained by a reaction between a polyol and an excess of an isocyanate compound can also be used.
  • the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
  • Examples of the (meth) acrylic acid derivative having a hydroxyl group include divalent alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
  • divalent alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
  • Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8411, EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220, KRM7735, KRM-8295 (both manufactured by Daicel Orunekusu, Inc.
  • radical polymerizable compounds other than those described above can be used as appropriate.
  • the other radical polymerizable compounds include N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N-hydroxyethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N -(Meth) acrylamide compounds such as isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, styrene, ⁇ -methylstyrene, N-vinyl-2-pyrrolidone, N-vinyl- ⁇ -caprolactam, etc.
  • a vinyl compound etc. are mentioned.
  • the radical polymerizable compound preferably contains a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound from the viewpoint of adjusting curability.
  • a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound By containing the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound, the resulting adhesive composition is more excellent in curability and tackiness.
  • urethane (meth) acrylate is preferably used in combination with the monofunctional radical polymerizable compound as the polyfunctional radical polymerizable compound.
  • the polyfunctional radically polymerizable compound is preferably bifunctional or trifunctional, and more preferably bifunctional.
  • the radical polymerizable compound contains the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound
  • the content of the polyfunctional radical polymerizable compound is the same as the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound.
  • a preferable lower limit is 2 parts by weight and a preferable upper limit is 45 parts by weight with respect to a total of 100 parts by weight with the functional radical polymerizable compound.
  • the content of the polyfunctional radically polymerizable compound is within this range, the resulting adhesive composition is more excellent in curability and tackiness.
  • the minimum with more preferable content of the said polyfunctional radically polymerizable compound is 5 weight part, and a more preferable upper limit is 35 weight part.
  • the preferable lower limit of the content of the radical polymerizable compound in 100 parts by weight of the adhesive composition of the present invention is 10 parts by weight, and the preferable upper limit is 80 parts by weight.
  • the content of the radical polymerizable compound is within this range, the resulting adhesive composition is excellent in both photocurability and moisture curability.
  • the minimum with more preferable content of the said radically polymerizable compound is 30 weight part, and a more preferable upper limit is 59 weight part.
  • photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthones, and the like.
  • photo radical polymerization initiators examples include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Benzylin TPO, all manufactured by BALGIN SPO.
  • Benzoin ethyl ether, benzoin isopropyl ether both manufactured by Tokyo Chemical Industry Co., Ltd.
  • the content of the photo radical polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the radical polymerizable compound. When the content of the photo radical polymerization initiator is within this range, the resulting adhesive composition is more excellent in photocurability and storage stability.
  • the minimum with more preferable content of the said radical photopolymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
  • the adhesive composition of the present invention preferably contains a wax.
  • the adhesive composition of the present invention is superior in reworkability because the foaming agent foams and the cured body softens due to heating during rework.
  • the “wax” means an organic substance that is solid at 23 ° C. and becomes liquid when heated.
  • the preferable lower limit of the melting point of the wax is 60 ° C., and the preferable upper limit is 130 ° C. When the melting point of the wax is within this range, the resulting adhesive composition is more excellent in the effect of achieving both adhesiveness and reworkability.
  • a more preferable lower limit of the melting point of the wax is 75 ° C., and a more preferable upper limit is 100 ° C.
  • the melting point of the wax can be determined by differential scanning calorimetry.
  • the wax include, for example, olefinic wax or paraffinic wax such as polypropylene wax, polyethylene wax, microcrystalline wax, and oxidized polyethylene wax, and aliphatic such as carnauba wax, sazol wax, and montanic ester wax.
  • olefinic wax or paraffinic wax such as polypropylene wax, polyethylene wax, microcrystalline wax, and oxidized polyethylene wax
  • aliphatic such as carnauba wax, sazol wax, and montanic ester wax.
  • Wax aromatic bisamide waxes such as m-xylenebisstearic acid amide and N, N'-distearylisophthalic acid amide, graft modified waxes obtained by graft polymerization of vinyl monomers such as styrene onto polyolefins, behenic acid Monoglyceride Ester waxes obtained by reacting various fatty acids with polyhydric alcohols, methyl ester waxes having hydroxyl groups obtained by hydrogenating vegetable oils and fats, and ethylene-vinyl acetate copolymer waxes having a high ethylene component content And long-chain alkyl acrylate waxes such as saturated stearyl acrylate waxes such as acrylic acid, and aromatic acrylate waxes such as benzyl acrylate waxes. Of these, paraffin wax and sazol wax are preferable.
  • HS crystal 6100 HS crystal 7100 (all manufactured by Toyokuni Oil Co., Ltd.), H1, H1N6, C105, H105, C80, spray 30, spray 105 (all manufactured by Sasol) Manufactured), ParaffinWax-155, ParaffinWax-150, ParaffinWax-145, ParaffinWax-140, HNP-3, HNP-9, HNP-51, SP-0165, Hi-Mic-2095, Hi-Mic-1090, Hi-Mic -1080, Hi-Mic-1070, NPS-6010, FT115, SX105, FNP-0090 (all manufactured by Nippon Seiwa Co., Ltd.) and the like.
  • the preferable lower limit of the content of the wax in 100 parts by weight of the adhesive composition of the present invention is 1 part by weight, and the preferable upper limit is 40 parts by weight.
  • the content of the wax is within this range, the resulting adhesive composition is more excellent in the effect of achieving both adhesiveness and reworkability.
  • the more preferable lower limit of the wax content is 5 parts by weight, and the more preferable upper limit is 20 parts by weight.
  • the adhesive composition of the present invention preferably contains a catalyst that accelerates the moisture curing reaction of the moisture curable resin. By containing the catalyst, the adhesive composition of the present invention is superior in moisture curability.
  • the catalyst include tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate, and tin octylate, triethylamine, U-CAT651M (manufactured by SANAPRO), U-CAT660M (SANAPRO).
  • tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate, and tin octylate, triethylamine, U-CAT651M (manufactured by SANAPRO), U-CAT660M (SANAPRO).
  • the preferable lower limit of the content of the catalyst in 100 parts by weight of the adhesive composition of the present invention is 0.01 part by weight, and the preferable upper limit is 5 parts by weight.
  • the more preferable lower limit of the content of the catalyst is 0.25 parts by weight, and the more preferable upper limit is 3 parts by weight.
  • the adhesive composition of the present invention preferably contains a filler.
  • the adhesive composition of the present invention has suitable thixotropy and can sufficiently retain the shape after coating.
  • the filler preferably has a primary particle diameter with a preferred lower limit of 1 nm and a preferred upper limit of 50 nm. When the primary particle diameter of the filler is within this range, the resulting adhesive composition is more excellent in applicability and shape retention after application.
  • the more preferable lower limit of the primary particle diameter of the filler is 5 nm
  • the more preferable upper limit is 30 nm
  • the still more preferable lower limit is 10 nm
  • the still more preferable upper limit is 20 nm.
  • the primary particle size of the filler can be measured by dispersing the filler in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS).
  • the filler may be present as secondary particles (a collection of a plurality of primary particles) in the adhesive composition of the present invention, and the preferred lower limit of the particle diameter of such secondary particles is 5 nm, A preferable upper limit is 500 nm, a more preferable lower limit is 10 nm, and a more preferable upper limit is 100 nm.
  • the particle diameter of the secondary particles of the filler can be measured by observing the adhesive composition of the present invention or a cured product thereof using a transmission electron microscope (TEM).
  • an inorganic filler is preferable, and examples thereof include silica, talc, titanium oxide, zinc oxide, calcium carbonate and the like. Among these, silica is preferable because the resulting adhesive composition is excellent in ultraviolet transmittance. These fillers may be used alone or in combination of two or more.
  • the filler is preferably subjected to a hydrophobic surface treatment.
  • a hydrophobic surface treatment By the hydrophobic surface treatment, the resulting adhesive composition is more excellent in shape retention after application.
  • the hydrophobic surface treatment include silylation treatment, alkylation treatment, and epoxidation treatment. Especially, since it is excellent in the effect which improves shape retainability, a silylation process is preferable and a trimethylsilylation process is more preferable.
  • Examples of the method for treating the filler with a hydrophobic surface include a method for treating the surface of the filler with a surface treatment agent such as a silane coupling agent.
  • a surface treatment agent such as a silane coupling agent.
  • the trimethylsilylated silica is prepared by synthesizing silica by a method such as a sol-gel method and spraying hexamethyldisilazane in a state where the silica is fluidized, or in an organic solvent such as alcohol or toluene. After adding silica, hexamethyldisilazane, and water, it can be produced by a method of evaporating and drying water and an organic solvent with an evaporator.
  • the preferable lower limit of the content of the filler in 100 parts by weight of the adhesive composition of the present invention is 1 part by weight, and the preferable upper limit is 20 parts by weight.
  • the content of the filler is within this range, the obtained adhesive composition is more excellent in applicability and shape retention after application.
  • the more preferred lower limit of the content of the filler is 2 parts by weight, the more preferred upper limit is 15 parts by weight, the still more preferred lower limit is 3 parts by weight, the still more preferred upper limit is 10 parts by weight, and the particularly preferred lower limit is 4 parts by weight. .
  • the adhesive composition of the present invention may contain a light shielding agent.
  • the adhesive composition of this invention becomes the thing excellent in light-shielding property, For example, when it uses for a display element, it can prevent light leakage.
  • the display device manufactured using the adhesive composition of the present invention blended with the above light-shielding agent has a high contrast without leaking light, because the adhesive composition has sufficient light-shielding properties, and excellent Image display quality.
  • the “light-shielding agent” means a material having an ability of hardly transmitting light in the visible light region.
  • the light-shielding agent examples include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Further, the light-shielding agent does not have to be black, and materials such as silica, talc, titanium oxide, and the like mentioned as fillers can be used as long as they have the ability to hardly transmit light in the visible light region. Included in the light shielding agent. Of these, titanium black is preferable.
  • Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing light shielding properties to the adhesive composition of the present invention, while having a property of transmitting light having a wavelength in the vicinity of the ultraviolet region. It is an agent. Therefore, the photo-curing property of the adhesive composition of the present invention can be improved by using a photo-radical polymerization initiator that can initiate a reaction with light having a wavelength (370 to 450 nm) that increases the transmittance of the titanium black.
  • the light shielding agent contained in the adhesive composition of the present invention is preferably a highly insulating material, and titanium black is also suitable as the highly insulating light shielding agent.
  • the titanium black preferably has an optical density (OD value) of 3 or more, and more preferably 4 or more.
  • the titanium black preferably has a blackness (L value) of 9 or more, more preferably 11 or more. The higher the light shielding property of the titanium black, the better. There is no particular upper limit to the OD value of the titanium black, but it is usually 5 or less.
  • the above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide
  • an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide
  • Surface-treated titanium black such as those coated with an inorganic component such as magnesium oxide can also be used.
  • what is processed with the organic component is preferable at the point which can improve insulation more.
  • titanium black examples include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like.
  • the preferable lower limit of the specific surface area of the titanium black is 5 m 2 / g
  • the preferable upper limit is 40 m 2 / g
  • the more preferable lower limit is 10 m 2 / g
  • the more preferable upper limit is 25 m 2 / g.
  • the preferable lower limit of the sheet resistance of the titanium black is 10 9 ⁇ / ⁇ when mixed with a resin (70% blending), and the more preferable lower limit is 10 11 ⁇ / ⁇ .
  • the primary particle diameter of the light-shielding agent is appropriately selected depending on the application, such as the distance between the substrates of the display element or the like, but a preferred lower limit is 30 nm and a preferred upper limit is 500 nm.
  • a preferred lower limit is 30 nm and a preferred upper limit is 500 nm.
  • the resulting adhesive composition is excellent in applicability to the substrate and workability without greatly increasing viscosity and thixotropy.
  • the more preferable lower limit of the primary particle diameter of the light shielding agent is 50 nm, and the more preferable upper limit is 200 nm.
  • the primary particle diameter of the light shielding agent can be measured in the same manner as the primary particle diameter of the filler.
  • the minimum with preferable content of the said light-shielding agent in 100 weight part of adhesive compositions of this invention is 0.05 weight part, and a preferable upper limit is 10 weight part.
  • a preferable upper limit is 10 weight part.
  • the content of the light-shielding agent is within this range, the obtained adhesive composition is superior in light-shielding properties while maintaining excellent drawing properties, adhesion to a substrate, and strength after curing.
  • the more preferable lower limit of the content of the light shielding agent is 0.1 parts by weight, the more preferable upper limit is 2 parts by weight, and the still more preferable upper limit is 1 part by weight.
  • the adhesive composition of the present invention may further contain additives such as a colorant, an ionic liquid, a solvent, metal-containing particles, and a reactive diluent as necessary.
  • additives such as a colorant, an ionic liquid, a solvent, metal-containing particles, and a reactive diluent as necessary.
  • Examples of the method for producing the adhesive composition of the present invention include a moisture curable resin and a foaming agent using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll. And a method of mixing a radically polymerizable compound and a photoradical polymerization initiator and additives to be added as necessary.
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll.
  • the adhesive composition of the present invention preferably has a water content of 100 ppm or less.
  • the water content is 100 ppm or less, the reaction between the moisture curable resin and water during storage can be suppressed, and the adhesive composition is more excellent in storage stability.
  • the water content is more preferably 80 ppm or less.
  • the water content can be measured by a Karl Fischer moisture measuring device.
  • the preferable lower limit of the viscosity measured at 25 ° C. and 1 rpm using a cone plate viscometer is 50 Pa ⁇ s, and the preferable upper limit is 1000 Pa ⁇ s.
  • the viscosity is within this range, the workability when the adhesive composition is applied to an adherend such as a substrate is improved.
  • a more preferable lower limit of the viscosity is 80 Pa ⁇ s, a more preferable upper limit is 500 Pa ⁇ s, and a still more preferable upper limit is 400 Pa ⁇ s.
  • paintability can be improved by heating at the low temperature which does not foam a foaming agent at the time of application
  • the preferable lower limit of the thixotropic index of the adhesive composition of the present invention is 1.3, and the preferable upper limit is 5.0.
  • the more preferable lower limit of the thixotropic index is 1.5, and the more preferable upper limit is 4.0.
  • the thixotropic index is a viscosity measured at 25 ° C. and 1 rpm using a cone plate viscometer, and measured at 25 ° C. and 10 rpm using a cone plate viscometer. It means the value divided by the viscosity.
  • the optical density (OD value) of a cured product having a thickness of 1 mm after curing is preferably 1 or more.
  • the OD value is 1 or more, the light shielding property is excellent, and when used in a display element, leakage of light can be prevented and high contrast can be obtained.
  • the OD value is more preferably 1.5 or more. The higher the OD value, the better.
  • the preferable upper limit of the OD value of the cured product is 4.
  • the OD value after hardening of the said adhesive composition can be measured using an optical densitometer.
  • the adhesive composition of the present invention can be easily peeled off by heating during rework after curing.
  • the preferable lower limit of the heating temperature during the rework is 60 ° C.
  • the preferable upper limit is 120 ° C.
  • a more preferable lower limit of the heating temperature during the rework is 75 ° C.
  • a more preferable upper limit is 110 ° C.
  • the cured product of the adhesive composition of the present invention is also one aspect of the present invention. Since the moisture-curable urethane resin is contained in the adhesive composition before curing, the cured product of the present invention has a urea bond and / or a urethane bond.
  • the component contained in the cured product of the present invention is a component contained in the adhesive composition of the present invention and a component that has been changed by a chemical reaction or the like when the adhesive composition of the present invention is cured.
  • An electronic component having a cured product of the adhesive composition of the present invention is also one aspect of the present invention.
  • the adhesive composition of the present invention exhibits the excellent effects described above, particularly in electronic components that require downsizing and narrow frame design.
  • the adhesive composition of the present invention is mainly used for bonding adherends.
  • adherends such as metal, glass, and plastic.
  • shape of the adherend include a film shape, a sheet shape, a plate shape, a panel shape, a tray shape, a rod (rod-like body) shape, a box shape, and a housing shape.
  • Examples of the metal include steel, stainless steel, aluminum, copper, nickel, chromium, and alloys thereof.
  • Examples of the glass include alkali glass, non-alkali glass, and quartz glass.
  • Examples of the plastic include polyolefin resins such as high density polyethylene, ultra high molecular weight polyethylene, isotactic polypropylene, syndiotactic polypropylene, and ethylene propylene copolymer resin, nylon 6 (N6), nylon 66 (N66), Nylon 46 (N46), Nylon 11 (N11), Nylon 12 (N12), Nylon 610 (N610), Nylon 612 (N612), Nylon 6/66 copolymer (N6 / 66), Nylon 6/66/610 Polymer (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, polyamide 66 resin such as nylon 66 / PPS copo
  • Aromatic polyester resins polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, polynitrile such as methacrylonitrile / styrene / butadiene copolymer Resin, polycarbonate, polymethacrylate resin such as polymethyl methacrylate (PMMA), polyethyl methacrylate, ethylene / vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), vinyl alcohol And polyvinyl resins such as vinyl / ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, and the like. .
  • PMMA polymethyl methacrylate
  • EVA polyvin
  • Examples of the adherend include a composite material having a metal plating layer on the surface, and examples of the base material for plating the composite material include the metal, glass, and plastic described above. Furthermore, examples of the adherend include materials in which a passivation film is formed by passivating a metal surface. Examples of the passivating treatment include heat treatment and anodizing treatment. . In particular, in the case of an aluminum alloy or the like whose material is an international aluminum alloy name in the 6000 series, the adhesiveness can be improved by performing a sulfuric acid alumite treatment or a phosphoric acid alumite treatment as the passivation treatment.
  • first substrate, the second substrate, and a cured product of the adhesive composition of the present invention are included, and at least a part of the first substrate includes at least a part of the second substrate and the above-described second substrate.
  • An assembly part joined through a cured body of the adhesive composition is also one aspect of the present invention.
  • the first substrate and the second substrate each preferably include at least one electronic component.
  • the adhesive composition which is excellent in adhesiveness and can be easily reworked at low temperature can be provided.
  • the electronic component and assembly component which have the hardening body of this adhesive composition, and the hardening body of this adhesive composition can be provided.
  • (A) It is a schematic diagram which shows the adhesion state of the to-be-adhered body by the adhesive composition of this invention in case the thickness of an adhesive layer is small and (b) large.
  • (A) is a schematic diagram which shows the case where the sample for adhesive evaluation is seen from the top
  • (b) is a schematic diagram which shows the case where the sample for adhesive evaluation is seen from the side.
  • Examples 1 to 7, Comparative Examples 1 to 3 In accordance with the blending ratio described in Table 1, each material was stirred with a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), and then uniformly mixed with a ceramic three roll. To 7 and Comparative Examples 1 to 3 were obtained.
  • a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”)
  • FIG. 2 is a schematic diagram showing a case where the adhesive evaluation sample is viewed from above (FIG. 2A), and a schematic diagram showing a case where the adhesive evaluation sample is viewed from the side (FIG. 2B). showed that.
  • the produced adhesion evaluation sample was pulled at a rate of 5 mm / sec in the shear direction, and an aluminum substrate and a glass plate The strength at the time of peeling was measured. Where the measured strength was 18N / cm 2 or more " ⁇ ", there in the case was 18N / cm 2 less than 14N / cm 2 or more " ⁇ ", 14N / cm 2 less than 10 N / cm 2 or more In this case, the adhesiveness was evaluated as “ ⁇ ” and “X” when less than 10 N / cm 2 .
  • a reliability evaluation sample was prepared in the same manner as the adhesion evaluation sample prepared in the evaluation of “(Adhesiveness)”.
  • the produced reliability evaluation sample was hung perpendicularly to the ground, and placed in an oven at 80 ° C. with a 300 g weight hung on the end of the aluminum substrate.
  • the adhesive composition which is excellent in adhesiveness and can be easily reworked at low temperature can be provided.
  • the electronic component and assembly component which have the hardening body of this adhesive composition, and the hardening body of this adhesive composition can be provided.

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PCT/JP2017/028836 2016-08-09 2017-08-08 接着剤組成物、硬化体、電子部品及び組立部品 WO2018030434A1 (ja)

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CN201780008422.5A CN108603091B (zh) 2016-08-09 2017-08-08 粘接剂组合物、固化体、电子部件和组装部件
KR1020187021253A KR102326096B1 (ko) 2016-08-09 2017-08-08 접착제 조성물, 경화체, 전자 부품 및 조립 부품
JP2017546263A JP6878289B2 (ja) 2016-08-09 2017-08-08 接着剤組成物、硬化体、電子部品及び組立部品

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