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 PDFInfo
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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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- 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
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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
- 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
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- 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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Abstract
Description
しかしながら、表示素子の小型化に伴い、充分に光の届かない部分に光硬化型樹脂組成物が塗布されることがあり、その結果、光の届かない部分に塗布された光硬化型樹脂組成物は硬化が不充分となるという問題があった。この問題は、狭額縁設計の表示素子において特に顕著であった。そこで、光の届かない部分に塗布された場合でも充分に硬化できる樹脂組成物として光熱硬化型樹脂組成物を用い、光硬化と熱硬化とを併用することも行われているが、高温での加熱により素子等に悪影響を与えるおそれがあった。
このような電子部品の接着に用いられる接着剤として、例えば、特許文献1には、数平均分子量が600~1000であるエポキシ化合物を含有する熱硬化型の接着剤が開示されている。しかしながら、特許文献1に開示されているような熱硬化型の接着剤は、熱により損傷する可能性のある電子部品の接着には適さないものであった。
本発明は、接着性に優れ、かつ、低温でのリワークが容易な接着剤組成物を提供することを目的とする。また、本発明は、該接着剤組成物の硬化体、並びに、該接着剤組成物の硬化体を有する電子部品及び組立部品を提供することを目的とする。
以下に本発明を詳述する。
本発明の接着剤組成物は、接着剤としての使用後、強固な接着力を有しながらも、リワークに際しては、比較的低温で加熱することにより接着部分を剥離させることができる、いわゆる熱剥離型接着剤組成物である。
上記発泡剤を含有することにより、本発明の接着剤組成物は、低温でのリワーク性に優れるものとなる。
上記「発泡剤」としては、例えば、無機発泡剤、有機発泡剤、熱膨張性粒子等が挙げられる。上記発泡剤の形状は特に限定されないが、粒子形状であることが好ましい。
なお、上記「無機発泡剤」及び上記「有機発泡剤」は、加熱による分解等の作用によりガスを発生させるものを意味する。また、上記「熱膨張性粒子」は、熱可塑性樹脂からなるシェル内にコア剤として低沸点化合物を内包してなり、加熱によりコア剤が揮発してシェル内のガス圧が増し、シェルを構成する熱可塑性樹脂が軟化して体積が増大する粒子を意味する。
上記被覆層の被覆率の実質的な上限は100%である。
なお、上記微粒子の平均粒子径は、レーザー回折散乱法により測定することができる。レーザー回折散乱法には、例えば、Mastersizer Hydro 2000SM(Malvern社製)等を用いることができる。
上記微粒子の被覆率の実質的な上限は100%である。
なお、上記発泡剤の発泡開始温度は、熱機械分析装置(TMA)で上記発泡剤を加熱した際に、高さ方向の変位がプラスに転じたときの温度を意味する。
なお、上記発泡剤の平均粒子径は、レーザー回折散乱法により測定することができる。レーザー回折散乱法には、例えば、Mastersizer Hydro 2000SM(Malvern社製)等を用いることができる。
上記湿気硬化型樹脂としては、例えば、湿気硬化型ウレタン樹脂、加水分解性シリル基含有樹脂等が挙げられる。なかでも、湿気硬化型ウレタン樹脂が好ましい。
上記湿気硬化型ウレタン樹脂は、ウレタン結合とイソシアネート基とを有し、分子内のイソシアネート基が空気中又は被着体中の水分と反応して硬化する。
上記芳香族ポリイソシアネート化合物としては、例えば、ジフェニルメタンジイソシアネート、ジフェニルメタンジイソシアネートの液状変性物、ポリメリックMDI、トリレンジイソシアネート、ナフタレン-1,5-ジイソシアネート等が挙げられる。
上記脂肪族ポリイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、ノルボルナンジイソシアネート、トランスシクロヘキサン-1,4-ジイソシアネート、イソホロンジイソシアネート、水添キシリレンジイソシアネート、水添ジフェニルメタンジイソシアネート、シクロヘキサンジイソシアネート、ビス(イソシアネートメチル)シクロヘキサン、ジシクロヘキシルメタンジイソシアネート等が挙げられる。
上記ポリイソシアネート化合物としては、なかでも、蒸気圧及び毒性の低い点、扱いやすさの点からジフェニルメタンジイソシアネート及びその変性物が好ましい。
上記ポリイソシアネート化合物は、単独で用いられてもよいし、2種以上を組み合わせて用いられてもよい。
なお、lが0の場合とは、Rと結合した炭素が直接酸素と結合している場合を意味する。
上記加水分解性シリル基含有樹脂は、1分子中に加水分解性シリル基を1個のみ有していてもよいし、2個以上有していてもよい。なかでも、分子の主鎖両末端に加水分解性シリル基を有することが好ましい。
上記主鎖の骨格構造は特に限定されず、例えば、飽和炭化水素系重合体、ポリオキシアルキレン系重合体、(メタ)アクリル酸エステル系重合体等が挙げられる。
上記湿気硬化型樹脂が有していてもよいラジカル重合性官能基としては、不飽和二重結合を有する基が好ましく、特に反応性の面から(メタ)アクリロイル基がより好ましい。
なお、ラジカル重合性官能基を有する湿気硬化型樹脂は、後述するラジカル重合性化合物には含まず、湿気硬化型樹脂として扱う。
なお、本明細書において上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定を行い、ポリスチレン換算により求められる値である。GPCによってポリスチレン換算による重量平均分子量を測定する際のカラムとしては、例えば、Shodex LF-804(昭和電工社製)等が挙げられる。また、GPCで用いる溶媒としては、テトラヒドロフラン等が挙げられる。
図1に示されるように、被着体1を接着する接着剤組成物2からなる接着層の厚み3が大きいほど、単位面積4あたりの接着剤組成物2に存在する発泡剤5の量が多くなる。そのため、接着層の厚み3を、接着性を維持できる限度で大きな厚みとすることで、接着性とリワーク性とを両立する効果がより向上される。この場合、接着層の厚み3を維持するために、前処理として光硬化させることが好ましい。そこで、光硬化性を発現させるため、本発明の接着剤組成物は、ラジカル重合性化合物及び光ラジカル重合開始剤を含有することが好ましい。即ち、上記ラジカル重合性化合物及び上記光ラジカル重合開始剤を含有することにより、光硬化性と湿気硬化性とが担保され、接着性とリワーク性との両立がより効果的なものとなる。このような本発明の接着剤組成物は、特に表示素子用封止剤や狭額縁設計の筐体接続に用いる接着剤に好適に用いることができる。
なお、本明細書において、上記「(メタ)アクリロイル」は、アクリロイル又はメタクリロイルを意味し、上記「(メタ)アクリル」は、アクリル又はメタクリルを意味する。
なお、本明細書において、上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味する。また、上記ウレタン(メタ)アクリレートは、残存イソシアネート基を有さない。
上記ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、グリセリン、ソルビトール、トリメチロールプロパン、カーボネートジオール、ポリエーテルジオール、ポリエステルジオール、ポリカプロラクトンジオール等が挙げられる。
上記その他のラジカル重合性化合物としては、例えば、N,N-ジメチル(メタ)アクリルアミド、N-(メタ)アクリロイルモルホリン、N-ヒドロキシエチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N,N-ジメチルアミノプロピル(メタ)アクリルアミド等の(メタ)アクリルアミド化合物、スチレン、α-メチルスチレン、N-ビニル-2-ピロリドン、N-ビニル-ε-カプロラクタム等のビニル化合物等が挙げられる。
上記ワックスを含有することにより、本発明の接着剤組成物は、リワーク時の加熱により発泡剤が発泡するとともに硬化体が軟化するため、リワーク性により優れるものとなる。
なお、本明細書において、上記「ワックス」とは、23℃で固体であり、加温することで液体となる有機物を意味する。
なお、上記ワックスの融点は、示差走査熱量測定により求めることができる。
上記充填剤を含有することにより、本発明の接着剤組成物は、好適なチクソ性を有するものとなり、塗布後の形状を充分に保持することができる。
なお、上記充填剤の一次粒子径は、NICOMP 380ZLS(PARTICLE SIZING SYSTEMS社製)を用いて、上記充填剤を溶媒(水、有機溶媒等)に分散させて測定することができる。
また、上記充填剤は、本発明の接着剤組成物中において二次粒子(一次粒子が複数集まったもの)として存在する場合があり、このような二次粒子の粒子径の好ましい下限は5nm、好ましい上限は500nm、より好ましい下限は10nm、より好ましい上限は100nmである。上記充填剤の二次粒子の粒子径は、本発明の接着剤組成物又はその硬化物を、透過型電子顕微鏡(TEM)を用いて観察することにより測定することができる。
上記疎水性表面処理としては、シリル化処理、アルキル化処理、エポキシ化処理等が挙げられる。なかでも、形状保持性を向上させる効果に優れることから、シリル化処理が好ましく、トリメチルシリル化処理がより好ましい。
具体的には例えば、上記トリメチルシリル化処理シリカは、シリカをゾルゲル法等の方法で合成し、シリカを流動させた状態でヘキサメチルジシラザンを噴霧する方法や、アルコール、トルエン等の有機溶媒中にシリカとヘキサメチルジシラザンと水とを加えた後、水と有機溶媒とをエバポレーターで蒸発乾燥させる方法等により作製することができる。
上記遮光剤を含有することにより、本発明の接着剤組成物は、遮光性に優れるものとなり、例えば、表示素子に用いた場合に光漏れを防止することができる。また、上記遮光剤を配合した本発明の接着剤組成物を用いて製造した表示素子は、接着剤組成物が充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有するものとなる。
なお、本明細書において、上記「遮光剤」は、可視光領域の光を透過させ難い能力を有する材料を意味する。
上記チタンブラックは、光学濃度(OD値)が、3以上であることが好ましく、4以上であることがより好ましい。また、上記チタンブラックは、黒色度(L値)が9以上であることが好ましく、11以上であることがより好ましい。上記チタンブラックの遮光性は高ければ高いほど良く、上記チタンブラックのOD値に好ましい上限は特に無いが、通常は5以下となる。
なお、上記遮光剤の一次粒子径は、上記充填剤の一次粒子径と同様にして測定することができる。
なお、上記水分量は、カールフィッシャー水分測定装置により測定することができる。
なお、本発明の接着剤組成物の粘度が高すぎる場合は、塗布時に発泡剤が発泡しない程度の低温で加温することで塗布性を向上させることができる。
なお、本明細書において上記チクソトロピックインデックスとは、コーンプレート型粘度計を用いて25℃、1rpmの条件で測定した粘度を、コーンプレート型粘度計を用いて25℃、10rpmの条件で測定した粘度で除した値を意味する。
上記OD値は高いほど良いが、上記OD値を高くするために遮光剤を多く配合しすぎると、増粘による作業性の低下等が生じることから、遮光剤の配合量とのバランスをとるため、上記硬化体のOD値の好ましい上限は4である。
なお、上記接着剤組成物の硬化後のOD値は、光学濃度計を用いて測定することができる。
上記リワーク時の加熱温度の好ましい下限は60℃、好ましい上限は120℃である。上記加熱温度がこの範囲であることにより、電子部品等を損傷させることなく容易に剥離することができる。上記リワーク時の加熱温度のより好ましい下限は75℃、より好ましい上限は110℃である。
本発明の電子部品において、本発明の接着剤組成物は、主に被着体の接着に用いられる。
上記被着体の形状としては、例えば、フィルム状、シート状、板状、パネル状、トレイ状、ロッド(棒状体)状、箱体状、筐体状等が挙げられる。
上記ガラスとしては、例えば、アルカリガラス、無アルカリガラス、石英ガラス等が挙げられる。
上記プラスチックとしては、例えば、高密度ポリエチレン、超高分子量ポリエチレン、アイソタクチックポリプロピレン、シンジオタクチックポリプロピレン、エチレンプロピレン共重合体樹脂等のポリオレフィン系樹脂、ナイロン6(N6)、ナイロン66(N66)、ナイロン46(N46)、ナイロン11(N11)、ナイロン12(N12)、ナイロン610(N610)、ナイロン612(N612)、ナイロン6/66共重合体(N6/66)、ナイロン6/66/610共重合体(N6/66/610)、ナイロンMXD6(MXD6)、ナイロン6T、ナイロン6/6T共重合体、ナイロン66/PP共重合体、ナイロン66/PPS共重合体等のポリアミド系樹脂、ポリブチレンテレフタレート(PBT)、ポリエチレンテレフタレート(PET)、ポリエチレンイソフタレート(PEI)、PET/PEI共重合体、ポリアリレート(PAR)、ポリブチレンナフタレート(PBN)、液晶ポリエステル、ポリオキシアルキレンジイミドジ酸/ポリブチレンテレフタレート共重合体等の芳香族ポリエステル系樹脂、ポリアクリロニトリル(PAN)、ポリメタクリロニトリル、アクリロニトリル/スチレン共重合体(AS)、メタクリロニトリル/スチレン共重合体、メタクリロニトリル/スチレン/ブタジエン共重合体等のポリニトリル系樹脂、ポリカーボネート、ポリメタクリル酸メチル(PMMA)、ポリメタクリル酸エチル等のポリメタクリレート系樹脂、エチレン/酢酸ビニル共重合体(EVA)、ポリビニルアルコール(PVA)、ビニルアルコール/エチレン共重合体(EVOH)、ポリ塩化ビニリデン(PVDC)、ポリ塩化ビニル(PVC)、塩化ビニル/塩化ビニリデン共重合体、塩化ビニリデン/メチルアクリレート共重合体等のポリビニル系樹脂等が挙げられる。
更に、上記被着体としては、金属表面を不動態化処理することにより不動態皮膜を形成した材料も挙げられ、該不動態化処理としては、例えば、加熱処理、陽極酸化処理等が挙げられる。特に、国際アルミニウム合金名が6000番台の材質であるアルミニウム合金等の場合は、上記不動態化処理として硫酸アルマイト処理又はリン酸アルマイト処理を行うことで、接着性を向上させることができる。
上記第1の基板及び上記第2の基板は、それぞれ少なくとも1つの電子部品を有することが好ましい。
ポリオール化合物として100重量部のポリテトラメチレンエーテルグリコール(三菱化学社製、「PTMG-2000」)と、0.01重量部のジブチル錫ジラウレートとを500mL容のセパラブルフラスコに入れ、真空下(20mmHg以下)、100℃で30分間撹拌し、混合した。その後常圧とし、ポリイソシアネート化合物としてジフェニルメタンジイソシアネート(日曹商事社製、「Pure MDI」)26.5重量部を入れ、80℃で3時間撹拌して反応させ、湿気硬化型ウレタン樹脂(重量平均分子量2700)を得た。
表1に記載された配合比に従い、各材料を、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して実施例1~7、比較例1~3の接着剤組成物を得た。
実施例及び比較例で得られた各接着剤組成物について以下の評価を行った。結果を表1に示した。なお、比較例3で得られた接着剤組成物については、樹脂が硬化せず、各評価におけるサンプルの作製ができなかったため、以下の評価は行わなかった。
実施例及び比較例で得られた各接着剤組成物を、ディスペンス装置を用いて、アルミニウム基板に約1mmの幅で塗布し、UV-LED(波長365nm)を用いて、紫外線を1000mJ/cm2照射することによって光硬化させた。次いで、該アルミニウム基板にガラス板を貼り合わせ、100gの重りを置き、一晩放置することにより湿気硬化させて、接着性評価用サンプルを得た。
図2に接着性評価用サンプルを上から見た場合を示す模式図(図2(a))、及び、接着性評価用サンプルを横から見た場合を示す模式図(図2(b))を示した。
作製した接着性評価用サンプルを、25℃及び80℃において引張り試験機(島津製作所社製、「Ez-Graph」)を用いて、剪断方向に5mm/secの速度で引張り、アルミニウム基板とガラス板とが剥がれる際の強度を測定した。
測定された強度が18N/cm2以上であった場合を「◎」、18N/cm2未満14N/cm2以上であった場合を「○」、14N/cm2未満10N/cm2以上であった場合を「△」、10N/cm2未満であった場合を「×」として接着性を評価した。
上記「(接着性)」の評価で作製した接着性評価用サンプルと同様にして信頼性評価用サンプルを作製した。
作製した信頼性評価用サンプルを地面に対して垂直にぶら下げ、アルミニウム基板の端に300gの重りをつるした状態で80℃のオーブンに入れた。
オーブンに入れてから72時間以上経過してもアルミニウム基板とガラスとが剥がれていなかった場合を「◎」、24時間以上72時間未満で剥がれた場合を「○」、12時間以上24時間未満で剥がれた場合を「△」、12時間未満で剥がれていた場合を「×」として信頼性を評価した。
上記「(接着性)」の評価で作製した接着性評価用サンプルと同様にしてリワーク性評価用サンプルを得た。
作製したリワーク評価用サンプルを、100℃において引張り試験機(島津製作所社製、「Ez-Graph」)を用いて、剪断方向に5mm/secの速度で引張り、アルミニウム基板とガラス板とが剥がれる際の強度を測定した。
測定された強度が5N/cm2以下であった場合を「◎」、5N/cm2を超え10N/cm2以下であった場合を「○」、10N/cm2を超え18N/cm2以下であった場合を「△」、18N/cm2を超えた場合を「×」としてリワーク性を評価した。
2 接着剤組成物
3 接着層の厚み
4 単位面積
5 発泡剤
6 アルミニウム基板
7 接着剤組成物
8 ガラス板
Claims (11)
- 湿気硬化型樹脂と発泡剤とを含有することを特徴とする接着剤組成物。
- 前記発泡剤は、発泡開始温度が60℃~130℃であることを特徴とする請求項1記載の接着剤組成物。
- 前記発泡剤は、粒子形状であり、平均粒子径が5~20μmであることを特徴とする請求項1又は2記載の接着剤組成物。
- 前記接着剤組成物100重量部中における発泡剤の含有量が1~50重量部であることを特徴とする請求項1、2又は3記載の接着剤組成物。
- 前記湿気硬化型樹脂は、湿気硬化型ウレタン樹脂であることを特徴とする請求項1、2、3又は4記載の接着剤組成物。
- ラジカル重合性化合物及び光ラジカル重合開始剤を含有することを特徴とする請求項1、2、3、4又は5記載の接着剤組成物。
- ワックスを含有することを特徴とする請求項1、2、3、4、5又は6記載の接着剤組成物。
- 請求項1、2、3、4、5、6又は7記載の接着剤組成物の硬化体であって、ウレア結合及び/又はウレタン結合を有することを特徴とする硬化体。
- 請求項1、2、3、4、5、6又は7記載の接着剤組成物の硬化体を有することを特徴とする電子部品。
- 第1の基板、第2の基板、及び、請求項1、2、3、4、5、6又は7記載の接着剤組成物の硬化体を有し、
前記第1の基板の少なくとも一部は、前記第2の基板の少なくとも一部と前記接着剤組成物の硬化体を介して接合されていることを特徴とする組立部品。 - 前記第1の基板及び前記第2の基板は、それぞれ少なくとも1つの電子部品を有することを特徴とする請求項10記載の組立部品。
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