CN109072040B - Adhesive composition, cured body, electronic component, and assembled component - Google Patents
Adhesive composition, cured body, electronic component, and assembled component Download PDFInfo
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- CN109072040B CN109072040B CN201780024169.2A CN201780024169A CN109072040B CN 109072040 B CN109072040 B CN 109072040B CN 201780024169 A CN201780024169 A CN 201780024169A CN 109072040 B CN109072040 B CN 109072040B
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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
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Abstract
The invention aims to provide an adhesive composition which has excellent adhesiveness and is easy to reprocess at low temperature. Further, the present invention aims to provide a cured product of the adhesive composition, and an electronic component and an assembly component each having the cured product of the adhesive composition. The present invention is an adhesive composition containing a moisture-curable resin and a wax.
Description
Technical Field
The present invention relates to an adhesive composition which has excellent adhesiveness and is easy to rework at low temperature. The present invention also relates to a cured product of the adhesive composition, and an electronic component and an assembled component each having the cured product of the adhesive composition.
Background
In recent years, liquid crystal display elements, organic EL display elements, and the like have been widely used as display elements having features such as thin thickness, light weight, and low power consumption. In these display devices, a photocurable resin composition is generally used for sealing a liquid crystal or a light-emitting layer, bonding various members such as a substrate, an optical film, and a protective film, and the like. In addition, in the modern times in which various mobile devices with display elements such as mobile phones and portable game machines are widespread, the most demanding problem is the miniaturization of the display elements.
However, as the size of the display device is reduced, the photocurable resin composition may be applied to a portion which is not sufficiently reached by light, and as a result, there is a problem that the photocurable resin composition applied to the portion which is not sufficiently reached by light is insufficiently cured. Therefore, although a photo-thermal curable resin composition is used as a resin composition which can be sufficiently cured even when applied to a portion which is not reached by light, and photo-curing and thermal curing are used in combination, there is a concern that heating at a high temperature may adversely affect an element or the like.
In recent years, electronic components such as semiconductor chips are required to be highly integrated and downsized, and for example, a stack of semiconductor chips is formed by bonding a plurality of thin semiconductor chips with an adhesive layer interposed therebetween. Such a stacked body of semiconductor chips is manufactured by, for example, the following method: a method in which after an adhesive is applied to one semiconductor chip, another semiconductor chip is stacked via the adhesive, and thereafter the adhesive is cured; a method of filling the adhesive between the semiconductor chips held at a predetermined interval and then curing the adhesive.
As an adhesive used for bonding such electronic components, for example, patent document 1 discloses a thermosetting adhesive containing an epoxy compound having a number average molecular weight of 600 to 1000. However, the thermosetting adhesive disclosed in patent document 1 is not suitable for bonding electronic components that may be damaged by heat.
As a method for curing a resin composition without heating at a high temperature, a method using a moisture-curable resin composition has been studied. For example, patent document 2 discloses a moisture-curable resin composition which is cured by crosslinking by reacting an isocyanate group in a resin with moisture (moisture) in the air or in an adherend. However, the thermosetting adhesive disclosed in patent document 1 is not suitable for bonding electronic components that may be damaged by heat. In addition, when a thermosetting adhesive is subjected to a large load for a long time, the adhesive properties are likely to be degraded, and it is difficult to obtain an adhesive with high reliability.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2000-178342
Patent document 2: japanese patent laid-open publication No. 2002-212534
Disclosure of Invention
Problems to be solved by the invention
The present inventors have now conceived a novel moisture-curable resin composition which can impart reworkability, but it is difficult to achieve both adhesiveness and reworkability (removability) with the moisture-curable resin composition described above. In particular, when rework is performed under high temperature conditions, there is a problem that electronic components and the like are damaged, and therefore, it is necessary to study a resin composition which is cured without heating at high temperature at the time of fixing, has excellent adhesiveness, and can be easily peeled by heating at low temperature at the time of rework.
The invention aims to provide an adhesive composition which has excellent adhesiveness and is easy to reprocess at low temperature. The invention also provides a cured product of the adhesive composition, and an electronic component and an assembly component having the cured product of the adhesive composition.
Means for solving the problems
The present invention is an adhesive composition containing a moisture-curable resin and a wax.
The present invention is described in detail below.
The inventors of the present invention found that: the present inventors have found that an adhesive composition having excellent adhesiveness and easy reworking at low temperature can be obtained by blending a moisture-curable resin composition with a wax, and have completed the present invention.
The adhesive composition of the present invention contains wax.
The adhesive composition of the present invention contains the wax, and thus the cured product is softened by heating during reworking, and the adhesive strength is significantly reduced, thereby providing excellent reworkability.
In the present specification, the "wax" refers to an organic substance that is solid at 23 ℃ and becomes liquid by heating.
The melting point of the wax preferably has a lower limit of 50 ℃ and an upper limit of 140 ℃. By setting the melting point of the wax within the above range, the obtained adhesive composition has a further excellent effect of achieving both adhesiveness and reworkability. The melting point of the wax is more preferably 70 ℃ at the lower limit and 110 ℃ at the upper limit.
The melting point of the wax is set to a temperature at which the peak top of the endotherm is shown in a curve obtained by differential scanning calorimetry.
When the wax is present in the form of fine particles (hereinafter also referred to as "wax fine particles") in the adhesive composition of the present invention, the contact area between the resin and the wax is increased, and the resultant adhesive composition is more excellent in reworkability, and thus is suitable.
The smaller the particle diameter of the wax fine particles, the better, and the preferable upper limit is 300. Mu.m. By setting the particle diameter of the wax fine particles to 300 μm or less, the adhesive composition obtained is more excellent in reworkability. A more preferable upper limit of the particle diameter of the wax fine particles is 250. Mu.m, a further more preferable upper limit is 100. Mu.m, a further more preferable upper limit is 50 μm, and a particularly preferable upper limit is 10 μm.
The lower limit of the particle diameter of the wax fine particles is not particularly limited, and the lower limit is substantially 0.1 μm.
The particle size of the wax fine particles can be measured by, for example, a scanning electron microscope, a laser diffraction particle size distribution measuring device, a disk centrifugal particle size distribution measuring device, a number counting particle size distribution measuring device, or the like, when the wax fine particles as a raw material are measured. When wax fine particles present in the adhesive composition of the present invention are measured, the measurement can be performed by a scanning electron microscope, a transmission electron microscope, a laser microscope, or the like. As a preferable measurement method, a method using a "laser diffraction particle size distribution measuring apparatus" is used when measuring the wax fine particles as the raw material, and a method using a "scanning electron microscope" is used when measuring the wax fine particles present in the adhesive composition of the present invention.
Specific examples of the wax include olefin-based waxes or paraffin-based waxes such as polypropylene wax, polyethylene wax, microcrystalline wax and oxidized polyethylene wax, aliphatic ester-based waxes such as carnauba wax, sasol wax and montanate wax, deacidified carnauba wax, palmitic acid (バルチミン acid), saturated aliphatic acid-based waxes such as stearic acid and montanic acid, unsaturated aliphatic acid-based waxes such as brassidic acid (プラシジン acid), eleostearic acid and palinoic acid (バリナリン acid), saturated alcohol-based waxes or aliphatic alcohol-based waxes such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, lignoceryl alcohol and ceryl alcohol, saturated fatty acid-based waxes such as sorbitol, polyol-based waxes such as sorbitol, linoleamide, oleamide, lauric amide and other saturated fatty acid amide-based waxes, methylenebisstearamide, ethylenebisdecanoamide, ethylenebislauric amide and hexamethylenebisstearamide-based waxes, ethylenebisoleamide, hexamethylenebisoleamide and N, unsaturated acid amide waxes such as N ' -dioleyl adipic acid amide and N, N ' -dioleyl sebacic acid amide, aromatic bisamide waxes such as m-xylylene bisstearic acid amide and N, N ' -distearyl isophthalic acid amide, graft-modified waxes obtained by graft-polymerizing a vinyl monomer such as styrene to a polyolefin, partial ester waxes obtained by reacting a fatty acid with a polyhydric alcohol such as behenic acid monoglyceride, methyl ester waxes having a hydroxyl group obtained by hydrogenating a vegetable oil or fat, long-chain alkyl acrylate waxes such as ethylene/vinyl acetate copolymer waxes having a high ethylene content ratio, saturated acrylic acid stearate waxes such as acrylic acid, and the like, aromatic acrylate waxes such as benzyl acrylate wax, and the like. Among them, paraffin wax and saso wax are preferable.
Examples of commercially available products of the above waxes include HS Krista-6100, HS Krista-7100 (all Feng Guo manufactured by oil manufacturing Co., ltd.), H1N6, C105, H105, C80, SPRAY30, SPRAY105 (all manufactured by Sasol Co., ltd.), 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, and FNP-0090 (all manufactured by Japanese Seiki wax Co., ltd.).
The lower limit of the content of the wax in 100 parts by weight of the adhesive composition of the present invention is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight. When the content of the wax is in the above range, the obtained adhesive composition has an excellent effect of achieving both adhesiveness and reworkability. The lower limit of the content of the wax is more preferably 3 parts by weight, the upper limit is more preferably 40 parts by weight, the lower limit is more preferably 5 parts by weight, and the upper limit is more preferably 30 parts by weight.
The adhesive composition of the present invention contains a moisture-curable resin.
Examples of the moisture-curable resin include moisture-curable polyurethane resins and hydrolyzable silyl group-containing resins. Among them, moisture-curable polyurethane resins are preferable.
The moisture-curable polyurethane resin has a urethane bond and an isocyanate group, and the isocyanate group in a molecule reacts with moisture in the air or in an adherend to cure the resin.
The moisture-curable polyurethane resin may have only 1 isocyanate group in 1 molecule, or may have 2 or more isocyanate groups. Among these, it is preferable to have isocyanate groups at both ends of the main chain of the molecule.
The moisture-curable polyurethane resin can be obtained by: the polyol compound having 2 or more hydroxyl groups in 1 molecule, and the polyisocyanate compound having 2 or more isocyanate groups in 1 molecule.
The reaction of the polyol compound and the polyisocyanate compound is usually carried out in a range in which a hydroxyl group (OH) in the polyol compound and an isocyanate group (NCO) in the polyisocyanate compound are [ NCO ]/[ OH ] =2.0 to 2.5 in a molar ratio.
As the polyol compound to be a raw material of the moisture-curable polyurethane resin, known polyol compounds generally used in the production of polyurethane can be used, and examples thereof include polyester polyol, polyether polyol, polyalkylene polyol, polycarbonate polyol and the like. These polyol compounds may be used alone, or 2 or more of them may be used in combination.
Examples of the polyester polyol include a polyester polyol obtained by reacting a polycarboxylic acid with a polyhydric alcohol, and a poly-e-caprolactone polyol obtained by ring-opening polymerization of e-caprolactone.
Examples of the polycarboxylic acid which is a raw material of the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, dodecamethylenedicarboxylic acid, and the like.
Examples of the polyhydric alcohol which is a raw material of the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and cyclohexanediol.
Examples of the polyether polyol include ring-opened polymers of ethylene glycol, propylene glycol and tetrahydrofuran, ring-opened polymers of 3-methyltetrahydrofuran, random copolymers or block copolymers of these and derivatives thereof, and bisphenol-type polyoxyalkylene modifications.
The bisphenol-type polyoxyalkylene modified product is a polyether polyol obtained by addition reaction of an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to an active hydrogen moiety of a bisphenol-type molecular skeleton, and may be a random copolymer or a block copolymer. The bisphenol-type polyoxyalkylene modified product is preferably obtained by adding 1 or 2 or more kinds of alkylene oxide to both ends of a bisphenol-type molecular skeleton. The bisphenol type is not particularly limited, and examples thereof include A type, F type, S type and the like, and bisphenol A type is preferable.
Examples of the polyalkylene polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.
Examples of the polycarbonate polyol include a polyhexamethylene carbonate polyol, a polycyclohexane dimethanol carbonate polyol, and the like.
As the polyisocyanate compound to be a raw material of the moisture-curable polyurethane resin, an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound can be suitably used.
Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, polymeric MDI, toluene diisocyanate, naphthalene-1,5-diisocyanate, and the like.
Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, and the like.
Among the polyisocyanate compounds, diphenylmethane diisocyanate and modified products thereof are preferred from the viewpoint of low vapor pressure and toxicity and from the viewpoint of ease of handling.
The polyisocyanate compounds may be used alone or in combination of 2 or more.
Further, the moisture-curable polyurethane resin is preferably a moisture-curable polyurethane resin obtained by using a polyol compound having a structure represented by the following formula (1). By using a polyol compound having a structure represented by the following formula (1), a composition having excellent adhesiveness and a cured product which is soft and has good elongation can be obtained, and the cured product has excellent compatibility with a radical polymerizable compound described later.
Among them, polyether polyols containing 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 preferably used.
In the formula (1), R represents a hydrogen atom, a methyl group or an ethyl group, 1 is an integer of 0 to 5, m is an integer of 1 to 500, and n is an integer of 1 to 10. 1 is preferably 0 to 4,m is preferably 50 to 200, and n is preferably 1 to 5.
The case where 1 is 0 means the case where the carbon bonded to R is directly bonded to oxygen.
The hydrolyzable silyl group in the molecule of the hydrolyzable silyl group containing resin reacts with moisture in the air or in the adherend to be cured.
The hydrolyzable silyl group-containing resin may have only 1 hydrolyzable silyl group in 1 molecule, or may have 2 or more hydrolyzable silyl groups. Among them, the molecule preferably has hydrolyzable silyl groups at both ends of the main chain.
The hydrolyzable silyl group is represented by the following formula (2).
-SiR 1 3-a X a (2)
In the formula (2), R 1 Each 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 (R 2 Each independently a hydrocarbon group having 1 to 20 carbon atoms). In the formula (2), each X is independently a hydroxyl group or a hydrolyzable group. In the formula (2), 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 aminoxy group, and a mercapto group. Among them, a halogen atom, an alkoxy group, an alkenyloxy group, and an acyloxy group are preferable from the viewpoint of high activity, and an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is further more preferable, from the viewpoint of stable hydrolyzability and easy handling. In addition, from the viewpoint of safety, the compounds to be desorbed by the reaction are preferably ethanol, an ethoxy group of acetone, and an isopropenyloxy group, respectively.
The hydroxyl group or the hydrolyzable group may be bonded within a range of 1 to 3 with respect to 1 silicon atom. When 2 or more hydroxyl groups or hydrolyzable groups are bonded to 1 silicon atom, these groups may be the same or different.
From the viewpoint of curability, a in the formula (2) is preferably 2 or 3, and particularly preferably 3. In addition, a is preferably 2 from the viewpoint of storage stability.
R in the above formula (2) 1 Examples thereof include alkyl groups such as methyl and ethyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, aralkyl groups such as benzyl, trimethylsiloxy groups, chloromethyl groups, and methoxymethyl groups. Among them, methyl is preferred.
Examples of the hydrolyzable silyl group include a methyldimethoxysilyl group, a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (dichloromethyl) dimethoxysilyl group, (1-chloroethyl) dimethoxysilyl group, (1-chloropropyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (ethoxymethyl) dimethoxysilyl group, (1-methoxyethyl) dimethoxysilyl group, (aminomethyl) dimethoxysilyl group, (N, N-dimethylaminomethyl) dimethoxysilyl group, (N, N-diethylaminomethyl) diethoxysilyl group, (N- (2-aminoethyl) aminomethyl) dimethoxysilyl group, (acetoxymethyl) dimethoxysilyl group, and (acetoxymethyl) diethoxysilyl group.
Examples of the hydrolyzable silyl group-containing resin include a hydrolyzable silyl group-containing (meth) acrylic resin, an organic polymer having a hydrolyzable silyl group at a molecular chain end or a molecular chain end portion, and a hydrolyzable silyl group-containing polyurethane resin.
The hydrolyzable silyl group-containing (meth) acrylic resin preferably has a repeating structural unit derived from a hydrolyzable silyl group-containing (meth) acrylate and an alkyl (meth) acrylate in the main chain.
Examples of the hydrolyzable silyl group-containing (meth) acrylate include 3- (trimethoxysilyl) propyl (meth) acrylate, 3- (triethoxysilyl) propyl (meth) acrylate, 3- (methyldimethoxysilyl) propyl (meth) acrylate, 2- (trimethoxysilyl) ethyl (meth) acrylate, 2- (triethoxysilyl) ethyl (meth) acrylate, 2- (methyldimethoxysilyl) ethyl (meth) acrylate, trimethoxysilylmethyl (meth) acrylate, triethoxysilylmethyl (meth) acrylate, and (methyldimethoxysilyl) methyl (meth) acrylate.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, and stearyl (meth) acrylate.
Specific examples of the method for producing the hydrolyzable silyl group-containing (meth) acrylic resin include a method for synthesizing a hydrolyzable silyl group-containing (meth) acrylate polymer as described in international publication No. 2016/035718.
The organic polymer having a hydrolyzable silyl group at a molecular chain end or a molecular chain end portion has a hydrolyzable silyl group at least one of a main chain end and a side chain end.
The backbone structure of the main chain is not particularly limited, and examples thereof include saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth) acrylate polymers.
Examples of the polyoxyalkylene polymer include polymers having a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, a polyoxyethylene-polyoxypropylene copolymer structure, and a polyoxypropylene-polyoxybutylene copolymer structure.
Specific examples of the method for producing the organic polymer having a hydrolyzable silyl group at the molecular chain end or molecular chain end site include a method for synthesizing an organic polymer having a crosslinkable silyl group only at the molecular chain end or molecular chain end site as described in, for example, international publication No. 2016/035718. Further, as another method for producing the organic polymer having a hydrolyzable silyl group at the molecular chain end or the molecular chain end portion, for example, a method for synthesizing a reactive silyl group-containing polyoxyalkylene polymer described in international publication No. 2012/117902, and the like can be given.
Examples of the method for producing the hydrolyzable silyl group-containing polyurethane resin include a method in which, for example, when a polyurethane resin is produced by reacting a polyol compound with a polyisocyanate compound, a silyl group-containing compound such as a silane coupling agent is further reacted. Specifically, for example, a method for synthesizing a urethane oligomer having a hydrolyzable silyl group is described in Japanese patent laid-open publication No. 2017-48345.
Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β -methoxy-ethoxy) silane, β - (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropylmethyldiethoxysilane, γ -methacryloxypropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethyldimethoxysilane, N-phenyl- γ -aminopropyltrimethoxysilane, γ -chloropropyltrimethoxysilane, γ -mercaptopropyltrimethoxysilane, γ -aminopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like. Among them, gamma-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane are preferable. These silane coupling agents may be used alone, or 2 or more of them may be used in combination.
Further, the moisture-curable resin may have a radical polymerizable functional group.
The radical polymerizable functional group optionally contained in the moisture-curable resin is preferably a group having an unsaturated double bond, particularly 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 the lower limit is preferably 800 and the upper limit is preferably 1 ten thousand. When the weight average molecular weight of the moisture-curable resin is in the above range, the obtained adhesive composition does not have an excessively high crosslinking density during curing, and has more excellent flexibility and more excellent coatability. The weight average molecular weight of the moisture-curable resin has a more preferable lower limit of 2000, a more preferable upper limit of 8000, a further preferable lower limit of 2500, and a further preferable upper limit of 6000.
In the present specification, the weight average molecular weight is a value measured by Gel Permeation Chromatography (GPC) and determined based on polystyrene conversion. 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 K.K.). Examples of the solvent used in GPC include tetrahydrofuran.
The lower limit of the content of the moisture-curable resin in 100 parts by weight of the adhesive composition of the present invention is preferably 20 parts by weight, and the upper limit is preferably 90 parts by weight. When the content of the moisture-curable resin is in the above range, the obtained adhesive composition can maintain excellent weather resistance and flexibility of a cured product, and has more excellent moisture curability. The lower limit of the content of the moisture-curable resin is more preferably 30 parts by weight, and the upper limit is more preferably 70 parts by weight.
The present inventors have studied increasing the thickness of an adhesive layer containing the adhesive composition of the present invention in order to further improve the effect of achieving both adhesiveness and reworkability, with the aim of increasing the amount of wax per unit area in contact with an adherend. Fig. 1 is a schematic view showing the adhered state of an adherend using the adhesive composition of the invention when (a) the thickness of the adhesive layer is small and (b) the thickness of the adhesive layer is large.
As shown in fig. 1, the larger the thickness 3 of the adhesive layer formed of the adhesive composition 2 for bonding the adherend 1, the more the amount of the wax 5 present in the adhesive composition 2 per unit area 4 becomes. Therefore, by setting the thickness 3 of the adhesive layer to a large thickness within a limit that can maintain the adhesiveness, the effect of achieving both the adhesiveness and the reworkability is further improved. In this case, it is preferable to perform photocuring as a pretreatment in order to maintain the thickness 3 of the adhesive layer. Therefore, in order to exhibit photocurability, the adhesive composition of the present invention preferably contains a radical polymerizable compound and a photoradical polymerization initiator. That is, by containing the radical polymerizable compound and the photo radical polymerization initiator, photocurability and moisture curability are ensured, and adhesiveness and reworkability can be more effectively achieved at the same time. The adhesive composition of the present invention can be suitably used in a sealant for a display element and an adhesive for connecting a frame body having a narrow frame edge design.
The radical polymerizable compound is not particularly limited as long as it is a radical polymerizable compound having photopolymerization properties, and as long as it is a compound having a radical polymerizable functional group in a molecule. Among them, a compound having an unsaturated double bond as a radical polymerizable functional group is suitable, and particularly, a compound having a (meth) acryloyl group (hereinafter, also referred to as a "(meth) acrylic compound") is suitable from the viewpoint of reactivity.
In the present specification, the "(meth) acryloyl group" means acryloyl group or methacryloyl group, and the "(meth) acrylic group" means acrylic group or methacrylic group.
Examples of the (meth) acrylic compound include a (meth) acrylate compound, an epoxy (meth) acrylate, and a urethane (meth) acrylate.
In the present specification, the "(meth) acrylate" refers to an acrylate or a methacrylate. The urethane (meth) acrylate has no remaining isocyanate group.
Examples of the monofunctional compound in the above-mentioned (meth) acrylate compound include phthalimide acrylates such as N-acryloyloxyethylhexahydrophthalimide, various imide (meth) acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, N-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethylcarbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1h, 5h-octafluoropentyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate and the like.
<xnotran> , () 2 , 5363 zxft 5363- () , 3242 zxft 3242- () , 4736 zxft 4736- () , 8978 zxft 8978- () ,1, 10- () ,2- -2- -6253 zxft 6253- () , () , () , () , () , () , () , () , A () , A () , F () , () , () , () ,2- -3- () () , () , () , </xnotran> Polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) acrylate, and the like.
Examples of the 3-or more-functional compound in the (meth) acrylate compound include 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, tri (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
Examples of the epoxy compound to be used 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, 2,2' -diallylbisphenol a type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition type bisphenol a type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidyl amine type epoxy resin, alkyl polyhydric epoxy resin, rubber modified type epoxy resin, glycidyl ester compound, bisphenol a alcohol type sulfur resin, and the like.
Examples of commercially available Epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182 (all made by Daicel-Allnex), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all made by Nakamura chemical Co., ltd.), epoxy Ester M-600A, epoxy Ester 40EM, epoxy Ester 70PA, epoxy Ester 200PA, epoxy Ester 80A, epoxy Ester 3002M, epoxy Ester 3002A, epoxy Ester 1600A, epoxy Ester 3000A (all made by Acrolea-3000 Co., ltd.), and Epoxy Ester DA 3000 (Deepoxy Ester A-3000, deepoxy Ester DA 3000, deepoxy Ester A, epoxy Ester DA 3000, epoxy Ester DA, and the like).
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 compound.
Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene 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 diisocyanate, 1,6, 11-undecane triisocyanate, and the like.
Further, as the isocyanate compound, an isocyanate compound having a chain extended by a reaction of a polyol and an excess amount of the isocyanate compound may be used.
Examples of the polyhydric alcohol 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 mono (meth) acrylates of diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol, mono (meth) acrylates or di (meth) acrylates of triols such as trimethylolethane, trimethylolpropane, and glycerol, and epoxy (meth) acrylates such as bisphenol a type epoxy (meth) acrylates.
Among the urethane (meth) acrylates, commercially available products, examples thereof include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toyo Synthesis Co., ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8411, EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL 7, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220, KRM7735, KRM-8295 (all manufactured by Daicel-Allnex Co., ltd.), art Resin UN-9000H, art Resin UN-9000A, art Resin-7100, art Resin-5, arcRYL 33500, artRYL 33500, arcRYL 330, arcRYL 3300, and ArcRYL U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U-108A, U-324A, U-340 zxft 3434-340P, U-1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201 1 4924 zxft 24-7100, UA-7200, UA-W2A (all of the products of the Ningmura chemical industries, inc., AI-600, AH-600, AT-600, UA-101 zxft 42-8542 zxft 8583 zxft 6283-359843), TOW 2A, TOW-3524-41024, and so on (all of the same products of the chemical industries, inc. Co., ltd., TOW-3598306, xft 9843, xft 9824, tokayama-359843, tokayama-3524, and so on.
In addition, other radical polymerizable compounds than the above may also be suitably used.
Examples of the other radical polymerizable compounds include (meth) acrylamide compounds such as N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N-hydroxyethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N, N-dimethylaminopropyl (meth) acrylamide, and vinyl compounds such as styrene, α -methylstyrene, N-vinyl-2-pyrrolidone, and N-vinyl-e-caprolactam.
The radical polymerizable compound preferably contains a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound from the viewpoint of adjusting curability and the like. By containing the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound, the adhesive composition obtained is more excellent in curability and adhesiveness. Among these, a combination of a urethane (meth) acrylate as the polyfunctional radical polymerizable compound and the monofunctional radical polymerizable compound is preferably used. The polyfunctional radical polymerizable compound is preferably 2-functional or 3-functional, and more preferably 2-functional.
When the radical polymerizable compound contains the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound, the lower limit of the content of the polyfunctional radical polymerizable compound is preferably 2 parts by weight and the upper limit thereof is preferably 45 parts by weight with respect to 100 parts by weight of the sum of the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound. When the content of the polyfunctional radical polymerizable compound is in the above range, the obtained adhesive composition is more excellent in curability and adhesiveness. The lower limit of the content of the polyfunctional radical polymerizable compound is more preferably 5 parts by weight, and the upper limit is more preferably 35 parts by weight.
The lower limit of the content of the radical polymerizable compound in 100 parts by weight of the adhesive composition of the present invention is preferably 10 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the radical polymerizable compound is in the above range, the resulting adhesive composition is more excellent in both photocurability and moisture curability. The lower limit of the content of the radical polymerizable compound is more preferably 30 parts by weight, and the upper limit is more preferably 60 parts by weight.
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
Examples of commercially available products of the photo radical polymerization initiator include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, lucirin TPO (all manufactured by BASF corporation), benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by tokyo chemical industries).
The content of the photo radical polymerization initiator is preferably 0.01 parts by weight at the lower limit and 10 parts by weight at the upper limit to 100 parts by weight of the radical polymerizable compound. When the content of the photo radical polymerization initiator is in the above range, the obtained adhesive composition is more excellent in photocurability and storage stability. The content of the photo radical polymerization initiator is more preferably 0.1 part by weight in the lower limit and 5 parts by weight in the upper limit.
The adhesive composition of the present invention preferably contains a filler.
By containing the filler, the adhesive composition of the present invention has appropriate thixotropy and can sufficiently maintain the shape after application.
The lower limit of the primary particle diameter of the filler is preferably 1nm, and the upper limit is preferably 50nm. When the primary particle diameter of the filler is in the above range, the resulting adhesive composition is more excellent in coatability and shape retention after coating. The lower limit of the primary particle diameter of the filler is more preferably 5nm, the upper limit is more preferably 30nm, the lower limit is more preferably 10nm, and the upper limit is more preferably 20nm.
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 PARTICLE SIZING SYSTEMS).
The filler may be present in the adhesive composition of the present invention as secondary particles (particles in which a plurality of primary particles are aggregated), and the particle diameter of such secondary particles has a preferred lower limit of 5nm, a preferred upper limit of 500nm, a more preferred lower limit of 10nm, and a more preferred upper limit of 100nm. 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).
The filler is preferably an inorganic filler, and examples thereof include silica, talc, titanium oxide, zinc oxide, calcium carbonate, and the like. Among them, silica is preferable because the obtained adhesive composition is excellent in ultraviolet transmittance. These fillers may be used alone, or 2 or more kinds may be used in combination.
The filler is preferably subjected to hydrophobic surface treatment. The adhesive composition obtained by the hydrophobic surface treatment has more excellent shape retention after application.
Examples of the hydrophobic surface treatment include silylation treatment, alkylation treatment, and epoxidation treatment. Among them, from the viewpoint of excellent effect of improving the shape retention property, the silylation treatment is preferable, and the trimethylsilylation treatment is more preferable.
Examples of the method of subjecting the filler to the hydrophobic surface treatment include a method of treating the surface of the filler with a surface treatment agent such as a silane coupling agent.
Specifically, for example, the trimethylsilylated silica can be produced by the following method: a method of synthesizing silica by a sol-gel method or the like and spraying hexamethyldisilazane while allowing the silica to flow; a method in which silica, hexamethyldisilazane, and water are added to an organic solvent such as alcohol or toluene, and then the water and the organic solvent are evaporated and dried by an evaporator.
The lower limit of the content of the filler in 100 parts by weight of the adhesive composition of the present invention is preferably 1 part by weight, and the upper limit is preferably 20 parts by weight. When the content of the filler is in the above range, the obtained adhesive composition is more excellent in coatability and shape retention after coating. The lower limit of the content of the filler is more preferably 2 parts by weight, the upper limit is more preferably 15 parts by weight, the lower limit is more preferably 3 parts by weight, the upper limit is more preferably 10 parts by weight, and the lower limit is particularly preferably 4 parts by weight.
The adhesive composition of the present invention may contain a light-shading agent.
The adhesive composition of the present invention is excellent in light-shielding properties by containing the light-shielding agent, and can prevent light leakage when used in a display device, for example. In addition, in the display element manufactured using the adhesive composition of the present invention containing the light-screening agent, since the adhesive composition has sufficient light-shielding properties, light does not leak out, and thus the display element has high contrast and excellent image display quality.
In the present specification, the "light-screening agent" refers to a material having an ability to transmit light in the visible light range with difficulty.
Examples of the light-shading agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. The light-shading agent may not be black, and any material having an ability to transmit light in the visible light region with difficulty may be used, and materials exemplified as fillers such as silica, talc, and titanium oxide are also included in the light-shading agent. Among them, titanium black is preferable.
The titanium black has a higher transmittance for light in the vicinity of the ultraviolet region, particularly at a wavelength of 370 to 450nm, than the average transmittance for light having a wavelength of 300 to 800 nm.
That is, the titanium black is a light-shielding agent having a property of sufficiently shielding light having a wavelength in the visible light region to impart light-shielding properties to the adhesive composition of the present invention and transmitting light having a wavelength in the vicinity of the ultraviolet region. Therefore, the photo-curability of the adhesive composition of the present invention can be further increased by using, as the photo-radical polymerization initiator, a substance capable of initiating a reaction by light having a wavelength (370 to 450 nm) at which the transmittance of the titanium black becomes high. On the other hand, as the light-shading agent contained in the adhesive composition of the present invention, a material having high insulation is preferable, and as the light-shading agent having high insulation, titanium black is also preferable.
The optical density (OD value) of the titanium black is preferably 3 or more, and more preferably 4 or more. The degree of blackness (L value) of the titanium black is preferably 9 or more, and more preferably 11 or more. The higher the light-shielding property of the titanium black, the better, and the OD value of the titanium black is not particularly preferably limited, but is usually 5 or less.
The above titanium black can exhibit sufficient effects without being surface-treated, but a titanium black having a surface treated with an organic component such as a coupling agent, a titanium black having a surface treated with an inorganic component such as silica, titanium oxide, germanium oxide, alumina, zirconium oxide, or magnesium oxide, or the like can be used. Among them, those treated with an organic component are preferable in terms of further improving the insulating properties.
Examples of commercially available products of the titanium black include 12S, 13M-C, 13R-N (all manufactured by Mitsubishi corporation), and Tilack D (manufactured by Gibber chemical Co., ltd.).
The lower limit of the specific surface area of the titanium black is preferably 5m 2 A preferred upper limit of 40m 2 A more preferred lower limit is 10m 2 A more preferable upper limit is 25m 2 /g。
In addition, a preferable lower limit of the sheet resistance of the titanium black is 10 in the case of being mixed with a resin (70% blending) 9 Omega/□, with a more preferred lower limit of 10 11 Ω/□。
In the adhesive composition of the present invention, the primary particle size of the light-shading agent may be appropriately selected depending on the application, for example, the distance between substrates of a display element or less, and the lower limit is preferably 30nm, and the upper limit is preferably 500nm. By setting the primary particle size of the light-shading agent to the above range, the obtained adhesive composition is more excellent in coatability and workability to a substrate without significantly increasing viscosity and thixotropy. The lower limit of the primary particle size of the light-shading agent is more preferably 50nm, and the upper limit thereof is more preferably 200nm.
The primary particle size of the light-shading agent can be measured in the same manner as the primary particle size of the filler.
The preferable lower limit of the content of the light-shading agent in 100 parts by weight of the adhesive composition of the present invention is 0.05 parts by weight, and the preferable upper limit is 10 parts by weight. When the content of the light-shading agent is in the above range, the obtained adhesive composition can maintain excellent drawing properties, adhesion to a substrate or the like, and strength after curing, and is further excellent in light-shielding properties. The lower limit of the content of the light-shading agent is more preferably 0.1 part by weight, the upper limit is more preferably 2 parts by weight, and the upper limit is more preferably 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, if necessary.
Examples of the method for producing the adhesive composition of the present invention include a method of mixing a moisture-curable resin, wax, and, if necessary, a radical polymerizable compound, a photo-radical polymerization initiator, and additives using a mixer such as a homomixer, universal mixer, planetary mixer, kneader, 3-roll mill, and the like.
The adhesive composition of the present invention preferably contains water in an amount of 100ppm or less. By setting the moisture content to 100ppm or less, the reaction between the moisture-curable resin and moisture during storage can be suppressed, and the adhesive composition has more excellent storage stability. The water content is more preferably 80ppm or less.
The moisture content can be measured by a Karl Fischer moisture measuring device.
The viscosity of the adhesive composition of the present invention measured at 25 ℃ and 1rpm with a cone-plate viscometer has a preferred lower limit of 50 pas and a preferred upper limit of 1000 pas. When the viscosity is in the above range, the workability when the adhesive composition is applied to an adherend such as a substrate is further improved. A more preferable lower limit of the viscosity is 80Pa · s, a more preferable upper limit is 500Pa · s, and a further more preferable upper limit is 400Pa · s.
When the viscosity of the adhesive composition of the present invention is too high, the coating property can be improved by heating at the time of coating.
The thixotropic index of the adhesive composition of the present invention has a preferred lower limit of 1.3 and a preferred upper limit of 5.0. When the thixotropic index is in the above range, the adhesive composition is more excellent in workability when applied to an adherend such as a substrate. The lower limit of the thixotropic index is more preferably 1.5, and the upper limit is more preferably 4.0.
In the present specification, the thixotropic index is a value obtained by dividing a viscosity measured at 25 ℃ and 1rpm with a cone and plate viscometer by a viscosity measured at 25 ℃ and 10rpm with a cone and plate viscometer.
The optical density (OD value) of a cured product having a thickness of 1mm after curing of the adhesive composition of the present invention is preferably 1 or more. By setting the OD value to 1 or more, the light-shielding property is excellent, and when the liquid crystal display device is used for a display element, light leakage 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, but when too much light-shading agent is added to increase the OD value, the workability may be deteriorated due to thickening, and therefore, in order to balance the amount of light-shading agent added, the preferable upper limit of the OD value of the cured product is 4.
The OD value of the adhesive composition after curing can be measured using an optical densitometer.
The adhesive composition of the present invention can be easily peeled off by heating at the time of reprocessing after curing.
The heating temperature during the above-mentioned reprocessing is preferably 60 ℃ at the lower limit and 120 ℃ at the upper limit. By setting the heating temperature to the above range, the electronic component and the like can be easily peeled off without damaging them. The lower limit of the heating temperature during the above-mentioned reprocessing is more preferably 75 ℃ and the upper limit thereof is more preferably 110 ℃.
The cured product of the adhesive composition of the present invention is also one aspect of the present invention.
When the adhesive composition of the present invention contains a moisture-curable polyurethane resin before curing, the cured product of the present invention has a urea bond and/or a urethane bond. The components contained in the cured product of the present invention are components contained in the adhesive composition of the present invention and components in which the components are changed by a chemical reaction or the like at the time of curing the adhesive composition of the present invention.
The cured product of the present invention is suitable because, when the wax is present as the wax fine particles in the cured product, the contact area between the resin and the wax becomes large, and the reworkability is more excellent.
The smaller the particle diameter of the wax fine particles in the solidified material, the better, and the preferable upper limit is 300 μm. The fine wax particles have a particle diameter of 300 μm or less, and thus have excellent reworkability. The upper limit of the particle diameter of the wax fine particles in the solidified material is more preferably 250 μm, still more preferably 100 μm, yet more preferably 50 μm, and particularly preferably 10 μm.
The lower limit of the particle diameter of the wax fine particles in the solidified material is not particularly limited, and the lower limit is substantially 0.1 μm.
The particle size of the wax fine particles in the cured product can be measured by observing the cut surface of the cured product using a scanning electron microscope, a transmission electron microscope, a laser microscope, or the like. A preferable measurement method includes a method of exposing a cross section of the cured product using a cryomicrotome, observing the cross section using a scanning electron microscope, measuring the particle diameters of 50 particles selected at random, and calculating the average value.
For the cured body of the present invention, it is preferable that: in the temperature range of 60 ℃ to 130 ℃, the change ratio of the storage elastic modulus at a temperature interval of 10 ℃ at which the change ratio of the storage elastic modulus ((storage elastic modulus on the high temperature side)/(storage elastic modulus on the low temperature side)) is maximum is 0.6 or less. By setting the change ratio of the storage elastic modulus to 0.6 or less, the cured product of the present invention is excellent in adhesion stability at the time of adhesion and small in adhesion force at the time of rework, and therefore, the reworkability is further excellent. The upper limit of the change ratio of the storage elastic modulus is more preferably 0.55, and still more preferably 0.45.
For the cured body of the present invention, it is preferable that: in the differential scanning calorimetry, the amount of energy per unit time at the peak of the endotherm of the cured product is represented by a, the amount of energy per unit time of the moisture-curable resin at the measurement temperature of a is represented by B, the amount of energy per unit time of the wax at the measurement temperature of a is represented by C, and the content of the wax in the cured product is represented by X wt%, the following formula is satisfied.
(A-B)/(C×X/100)≥50
By satisfying the above formula, the cured product of the present invention is more excellent in reworkability.
A more preferable lower limit of (A-B)/(C X/100) is 60, and a still more preferable lower limit is 70.
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 can exhibit the above-described excellent effects particularly in electronic components that need to be miniaturized. In the electronic component of the present invention, the adhesive composition of the present invention is mainly used for adhesion of an adherend.
The adherend to be adhered by using the adhesive composition of the present invention includes various adherends such as metal, glass, and plastic.
Examples of the shape of the adherend include a film shape, a sheet shape, a plate shape, a panel shape, a tray shape, a rod (rod-shaped body) shape, a box shape, and a frame shape.
Examples of the metal include steel, stainless steel, aluminum, copper, nickel, chromium, and alloys thereof.
Examples of the glass include alkali glass, alkali-free glass, and quartz glass.
Examples of the plastic include polyolefin resins such AS high-density polyethylene, ultrahigh-molecular-weight polyethylene, isotactic polypropylene, syndiotactic polypropylene, and ethylene-propylene copolymer resins, polyamide resins such AS 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 copolymer (N6/66/610), nylon MXD6 (MXD 6), nylon 6T, nylon 6/6T copolymer, nylon 66/PP copolymer, and nylon 66/PPs copolymer, aromatic polyester resins such AS polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET/PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyethylene oxide diimide diacid/polybutylene terephthalate copolymer, polyacrylonitrile (PAN), polyvinyl acetate, acrylonitrile/styrene copolymer (AS), methyl methacrylate/styrene copolymer, polyethylene methacrylate/acrylonitrile copolymer (AS), and polyethylene methacrylate/acrylonitrile copolymer (EVA), and polymethyl methacrylate copolymer (EVA) and polymethyl methacrylate copolymer, and polyethylene resins such as polyvinyl alcohol (PVA), vinyl alcohol/ethylene copolymers (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride/vinylidene chloride copolymers, and vinylidene chloride/methyl acrylate copolymers.
Further, the adherend may be a composite material having a metal-plated layer on the surface thereof, and the primer plating material of the composite material may be, for example, the above-mentioned metal, glass, plastic, or the like.
Further, the adherend may be a material having a passivation film formed by passivating the metal surface, and examples of the passivation treatment include a heat treatment and an anodic oxidation treatment. In particular, in the case of an aluminum alloy such as an aluminum alloy named 6000 international aluminum alloy, the adhesiveness can be improved by performing alumite treatment with sulfuric acid or alumite treatment with phosphoric acid as the passivation treatment.
An assembly member including a 1 st substrate, a 2 nd substrate, and a cured product of the adhesive composition of the present invention, in which at least a part of the 1 st substrate and at least a part of the 2 nd substrate are joined to each other through the cured product of the adhesive composition, is also one aspect of the present invention.
Preferably, the 1 st substrate and the 2 nd substrate each have at least 1 electronic component.
Effects of the invention
The present invention can provide an adhesive composition which has excellent adhesion and is easily reworked at low temperatures. Further, the present invention can provide a cured product of the adhesive composition, and an electronic component and an assembled component having the cured product of the adhesive composition.
Drawings
Fig. 1 is a schematic view showing the adhered state of an adherend using the adhesive composition of the invention in the case where (a) the thickness of the adhesive layer is small and (b) the thickness of the adhesive layer is large.
Fig. 2 (a) is a schematic view showing a case where the sample for reworkability evaluation is viewed from above, and (b) is a schematic view showing a case where the sample for reworkability evaluation is viewed from the side.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Synthesis example 1 (preparation of moisture-curable polyurethane resin)
100 parts by weight of polytetramethylene ether glycol (PTMG-2000, manufactured by Mitsubishi chemical corporation) as a polyol compound and 0.01 part by weight of dibutyltin dilaurate were charged in a 500mL separable flask, and the mixture was stirred at 100 ℃ for 30 minutes under vacuum (20 mmHg or less) to mix them. Then, 26.5 parts by weight of diphenylmethane diisocyanate (product of Nissan Co., ltd. "Pure MDI") as a polyisocyanate compound was added under normal pressure, and the mixture was stirred at 80 ℃ for 3 hours to react, thereby obtaining a moisture-curable polyurethane resin (weight-average molecular weight 2700).
(examples 1 to 6, comparative example 1)
The respective materials were stirred by a planetary stirring apparatus (manufactured by Thinky, "ぁわとり taro") according to the mixing ratios shown in table 1, and then uniformly mixed by a ceramic 3-roll mill to obtain adhesive compositions of examples 1 to 6 and comparative example 1.
< evaluation >
The following evaluations were made for each of the adhesive compositions obtained in examples and comparative examples. The results are shown in Table 1.
(reworkability)
Each of the adhesive compositions obtained in examples and comparative examples was coated on a polycarbonate substrate with a width of about 2mm using a dispensing device. Then, the adhesive composition was irradiated with 1000mJ/cm using UV-LED (wavelength 365 nm) 2 The glass plate was bonded to a polycarbonate substrate by the ultraviolet ray of (3), and a 20g weight was placed thereon and left to stand overnight, whereby the glass plate was moisture-cured to obtain a sample for evaluation of reworkability.
Fig. 2 shows a schematic view showing a case where the sample for reworkability evaluation is viewed from above (fig. 2 (a)), and a schematic view showing a case where the sample for reworkability evaluation is viewed from the side (fig. 2 (b)).
The sample for evaluation of reworkability thus prepared was stretched at a speed of 5mm/sec in the shear direction at 25 ℃ and 100 ℃ using a tensile tester (manufactured by Shimadzu corporation, "Ez-Graph"), and the strength (adhesive strength) at which the polycarbonate substrate and the glass plate were peeled was measured. As a result, the reworkability was evaluated by assuming that the ratio of the adhesion strength at 100 ℃ to the adhesion strength at 25 ℃ ((adhesion strength at 100 ℃/adhesion strength at 25 ℃) was 0.3 or less as "excellent", the ratio of the adhesion strength at 100 ℃/adhesion strength at 25 ℃) was 0.3 or less as "o", the ratio of the adhesion strength at greater than 0.3 and 0.5 or less as "Δ", the ratio of the adhesion strength at greater than 0.5 and 0.7 or less as "x".
(ratio of change in storage modulus of elasticity)
Each of the adhesive compositions obtained in examples and comparative examples was poured into a Teflon (registered trademark) mold having a width of 3mm, a length of 30mm and a thickness of 1mm, and irradiated with 1000mJ/cm using a UV-LED (wavelength: 365 nm) 2 Ultraviolet rays, thereby photocuring it, and then left for 3 days, thereby moisture-curing it, thereby obtaining a cured body.
Using a dynamic viscoelasticity measurement device (DVA-200, manufactured by IT measurement and control corporation), in the deformation mode: stretching and setting strain: 1%, measurement frequency: 1Hz, temperature rise rate: the dynamic viscoelasticity of the obtained cured product was measured at a temperature of 40 to 150 ℃ at a rate of 5 ℃/min, and the storage elastic modulus at each temperature was determined. Regarding the obtained storage elastic modulus, the change ratio of the storage elastic modulus at a temperature interval of 10 ℃ at which the change amount of the storage elastic modulus is the largest in the temperature range of 60 ℃ to 130 ℃ is calculated by the following formula.
Change ratio of storage elastic modulus = (storage elastic modulus at high temperature side)/(storage elastic modulus at low temperature side)
(degree of influence of wax in calorimetric determination)
The cured product of each adhesive composition obtained in the same manner as in the above "(change ratio of storage elastic modulus)" and the wax monomer used in each adhesive composition were measured for a change in heat amount with a change in temperature using a differential scanning calorimetry apparatus (TA Instruments, "DSC Q100"). The influence of wax in the heat amount measurement was calculated by the following equation, where a represents the amount of energy per unit time at the peak of the heat absorption of the cured product, B represents the amount of energy per unit time of the moisture-curable resin at the measurement temperature of a, C represents the amount of energy per unit time of the wax at the measurement temperature of a, and X wt% represents the content of the wax in the cured product.
Degree of influence of wax in heat measurement = (A-B)/(C X/100)
The measurement of the change in heat was performed under the following measurement conditions, and the obtained measurement values were A, B and C, respectively.
< measurement conditions >
Atmosphere: nitrogen (flow 40 mL/min)
Temperature rise rate: 10 ℃/min
Sample amount: 10mg of
The adhesive composition obtained in comparative example 1 did not contain wax, and therefore the present evaluation was not performed.
[ Table 1]
Industrial applicability
The present invention can provide an adhesive composition which has excellent adhesion and can be easily reworked at low temperatures. Further, the present invention can provide a cured product of the adhesive composition, and an electronic component and an assembled component each having the cured product of the adhesive composition.
Description of the symbols
1. Adherend (adherend)
2. Adhesive composition
3. Thickness of adhesive layer
4. Unit area
5. Wax
6. Polycarbonate substrate
7. Adhesive composition
8. Glass plate
Claims (9)
1. A cured product of an adhesive composition which is subjected to photocuring as a pretreatment,
the adhesive composition contains a moisture-curable polyurethane resin having a urethane bond and an isocyanate group, a radical polymerizable compound, a photo radical polymerization initiator, and a wax,
wherein the wax is present in the binder composition in particulate form,
the adhesive composition has a viscosity of 50 pas to 1000 pas as measured with a cone-plate viscometer at 25 ℃ and 1rpm,
the particle diameter of the fine particles in the solidified material is 300 [ mu ] m or less.
2. A cured product of an adhesive composition which is subjected to photocuring as a pretreatment, wherein,
the adhesive composition contains a moisture-curable polyurethane resin having a urethane bond and an isocyanate group, a radical polymerizable compound, a photo radical polymerization initiator, and a wax,
wherein the wax is present in the binder composition in particulate form,
the adhesive composition has a viscosity of 50 pas to 1000 pas as measured with a cone-plate viscometer at 25 ℃ and 1rpm,
the cured body has a ratio of change in storage elastic modulus represented by (storage elastic modulus on the high temperature side)/(storage elastic modulus on the low temperature side) of 0.6 or less at a temperature interval of 10 ℃ at which the ratio of change in storage elastic modulus is greatest in a temperature range of 60 ℃ to 130 ℃.
3. A cured product of an adhesive composition which is subjected to photocuring as a pretreatment, wherein,
the adhesive composition comprises a moisture-curable polyurethane resin having a urethane bond and an isocyanate group, a radical polymerizable compound, a photo radical polymerization initiator and a wax,
wherein the wax is present in the binder composition in particulate form,
the adhesive composition has a viscosity of 50 Pa.s or more and 1000 Pa.s or less as measured with a cone-plate viscometer at 25 ℃ and 1rpm,
in the differential scanning calorimetry, assuming that the amount of energy per unit time at the peak of the endotherm of the cured product is A, the amount of energy per unit time of the moisture-curable resin at the measurement temperature of A is B, the amount of energy per unit time of the wax at the measurement temperature of A is C, and the content of the wax in the cured product is X% by weight, the following formula is satisfied,
(A-B)/(C×X/100)≥50。
4. the cured body according to any one of claims 1 to 3, wherein the wax has a melting point of 50 ℃ or more and 140 ℃ or less.
5. The cured product according to any one of claims 1 to 3, wherein the content of the wax is 1 part by weight or more and 50 parts by weight or less in 100 parts by weight of the adhesive composition.
6. The cured product according to claim 2 or 3, wherein the particle diameter of the fine particles is 300 μm or less.
7. An electronic component characterized by having the cured body according to any one of claims 1 to 6.
8. An assembled component comprising a 1 st substrate, a 2 nd substrate, and the cured body according to any one of claims 1 to 6,
at least a part of the 1 st substrate and at least a part of the 2 nd substrate are bonded via the cured body.
9. The assembly of claim 8, wherein each of the 1 st substrate and the 2 nd substrate has at least 1 electronic component.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2016-156503 | 2016-08-09 | ||
| JP2016156503 | 2016-08-09 | ||
| JP2016-177786 | 2016-09-12 | ||
| JP2016177786 | 2016-09-12 | ||
| JP2017011406 | 2017-01-25 | ||
| JP2017-011406 | 2017-01-25 | ||
| JP2017-082031 | 2017-04-18 | ||
| JP2017082031 | 2017-04-18 | ||
| PCT/JP2017/028837 WO2018030435A1 (en) | 2016-08-09 | 2017-08-08 | Adhesive composition, cured body, electronic component, and assembly component |
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| CN109072040B true CN109072040B (en) | 2023-02-03 |
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| KR102171296B1 (en) * | 2019-08-12 | 2020-10-28 | (주)구쎈일렉트릭 | Method for manufacturing hologram mirror |
| US11155723B2 (en) * | 2019-10-18 | 2021-10-26 | Mitsubishi Electric Research Laboratories, Inc. | On-orbit additive manufacturing of parabolic reflectors via solar photopolymerization |
| WO2023145776A1 (en) * | 2022-01-27 | 2023-08-03 | 積水化学工業株式会社 | Polymer film and laminated glass |
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| JPWO2018030435A1 (en) | 2019-06-13 |
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| KR102326096B1 (en) | 2021-11-12 |
| CN108603091A (en) | 2018-09-28 |
| CN109072040A (en) | 2018-12-21 |
| TW201823414A (en) | 2018-07-01 |
| JP6878289B2 (en) | 2021-05-26 |
| KR20190035597A (en) | 2019-04-03 |
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| TW201816028A (en) | 2018-05-01 |
| TWI826355B (en) | 2023-12-21 |
| JPWO2018030434A1 (en) | 2019-06-13 |
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