WO2016084960A1 - 粘着剤組成物及びそれを用いた粘着シート - Google Patents
粘着剤組成物及びそれを用いた粘着シート Download PDFInfo
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- WO2016084960A1 WO2016084960A1 PCT/JP2015/083487 JP2015083487W WO2016084960A1 WO 2016084960 A1 WO2016084960 A1 WO 2016084960A1 JP 2015083487 W JP2015083487 W JP 2015083487W WO 2016084960 A1 WO2016084960 A1 WO 2016084960A1
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- sensitive adhesive
- epoxy resin
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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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
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2463/00—Presence of epoxy resin
Definitions
- the present invention relates to a pressure-sensitive adhesive composition, and more specifically, a lightweight metal and a lightweight composite resin constituting a composite member of a vehicle body can be bonded with high strength, and the outside air temperature changes greatly, or contacts water or a snow melting agent. Even if it does, it is related with the adhesive composition which can hold
- Adhesives are required to have strength properties at the time of adhesion and strength retention characteristics over time, but especially when used for vehicle bodies, they are exposed to vibration, impact, changes in outside temperature, wind and rain, etc. Sometimes it is required to bond with higher strength and to maintain higher strength over time.
- thermosetting resin such as an epoxy resin is used as a general adhesive.
- This epoxy adhesive is said to have a slightly insufficient toughness although the mechanical strength of the cured resin itself is high.
- Patent Document 1 attempts to add flexibility to the epoxy adhesive by adding a thermoplastic resin or the like to the epoxy resin.
- the present invention has been made to meet the above requirements, and an object of the present invention is to provide a pressure-sensitive adhesive composition capable of maintaining excellent adhesive strength, and a pressure-sensitive adhesive sheet using the same.
- the pressure-sensitive adhesive composition according to the present invention for solving the above-described problems includes a core-shell structure including at least an epoxy resin, acrylic particles, and a curing agent, and the acrylic particles include butadiene rubber and polymethacrylate or polyacrylate. It is characterized by being.
- the epoxy resin can be configured to be a bisphenol A type epoxy resin.
- the acrylic particles can be configured to have an average particle size of 200 nm or less.
- the blending ratio of the acrylic particles when the total mass of the pressure-sensitive adhesive composition is 100%, can be 3% or more and 33% or less on a mass basis. .
- the acrylic particles can be configured to have a reactive functional group.
- the pressure-sensitive adhesive composition according to the present invention can be configured such that the reactive functional group is an epoxy group.
- the butadiene-based rubber and the polymethacrylate or polyacrylate of the acrylic particles can be configured to be epoxy-modified polymethacrylate or epoxy-modified polyacrylate.
- the pressure-sensitive adhesive sheet according to the present invention for solving the above-described problem includes a pressure-sensitive adhesive layer between the first release film and the second release film, and the pressure-sensitive adhesive layer includes an epoxy resin, acrylic particles, and a curing agent. At least, the acrylic particle is a core-shell structure having a butadiene rubber and polymethacrylate or polyacrylate.
- the epoxy resin can be configured to be a bisphenol A type epoxy resin.
- the pressure-sensitive adhesive sheet according to the present invention can be configured such that the acrylic particles have an average particle size of 200 nm or less.
- the blending ratio of the acrylic particles can be 3% or more and 33% or less on a mass basis.
- the acrylic particles can be configured to have a reactive functional group.
- the pressure-sensitive adhesive sheet according to the present invention can be configured so that the reactive functional group is an epoxy group.
- the butadiene rubber of the acrylic particles and the polymethacrylate or polyacrylate can be configured to be epoxy-modified polymethacrylate or epoxy-modified polyacrylate.
- FIG. 4 is a graph showing the temperature dependence of storage elastic modulus (E ′) and loss tangent (tan ⁇ ) of the pressure-sensitive adhesives obtained in Example 1 and Comparative Example 1.
- the pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet according to the present invention will be described in detail.
- the scope of the present invention includes the scope of the gist and is not limited to the following embodiments.
- the pressure-sensitive adhesive composition according to the present invention is a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive composition is a core-shell structure that includes at least an epoxy resin, acrylic particles, and a curing agent, and the acrylic particles include butadiene rubber and polymethacrylate or polyacrylate.
- this pressure-sensitive adhesive composition contains specific acrylic particles in the epoxy resin, excellent adhesive strength can be maintained by the action of the acrylic particles.
- This pressure-sensitive adhesive composition is particularly excellent even when the lightweight composite resin and the lightweight metal member can be bonded with high strength, and the outside air temperature changes greatly or comes into contact with water or a snow melting agent. Adhesive strength can be maintained.
- the adhesive portion is exposed to severe factors such as vibration, impact, changes in outside air temperature, wind and rain, contact with water and snow melting agent, etc.
- the FRP and aluminum are excellent in that they can be bonded with higher strength and can maintain higher strength over time.
- Epoxy resin The epoxy resin contained in the pressure-sensitive adhesive composition of the present invention is a prepolymer having at least one epoxy group or glycidyl group, which is cured by a crosslinking polymerization reaction in combination with a curing agent, and is a cured pressure-sensitive adhesive.
- Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin and other bisphenol type epoxy resins, novolak epoxy resins, cresol novolac epoxy resins and other novolak type epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, and triphenols.
- Aromatic or alicyclic epoxy resins such as methane type epoxy resins, alkyl-modified triphenol methane type epoxy resins, triazine core-containing epoxy resins, dicyclopentadiene-modified phenol type epoxy resins, etc.
- bisphenol A type epoxy resins which are rigid bifunctional epoxy resins having a bisphenol skeleton can be suitably used.
- bisphenol A type epoxy resins with a main chain of 0 to 1 are liquid at room temperature
- bisphenol A type epoxy resins with a main chain of 2 to 10 are at room temperature. It is solid.
- a bisphenol A type epoxy resin that is solid at room temperature melts rapidly and changes to a low-viscosity liquid when the temperature exceeds the melting point. Therefore, in the step of joining the adherends, the pressure-sensitive adhesive adheres to the adherend by heating and solidifies by solidifying the adhesive, whereby the adhesive strength can be increased.
- a bisphenol A type epoxy resin has a high crosslink density, high mechanical strength, good chemical resistance, high curability, and low hygroscopicity (because the free volume is small). As a result, the bonding strength between the adherends can be improved.
- the liquid bisphenol A-type epoxy resin may be included at normal temperature.
- the bisphenol A type epoxy resin those having a glass transition temperature in the range of 50 ° C. to 150 ° C. are preferable from the viewpoint of mechanical strength, heat resistance and film-forming property.
- examples of the bisphenol A type epoxy resin having a main chain of 2 to 10 that is solid at normal temperature include JER1001 manufactured by Japan Epoxy Resin Co., Ltd.
- a trifunctional or higher functional epoxy resin may be included.
- the tri- or higher functional epoxy resin includes an epoxy resin having a tris (hydroxyphenyl) methane structure, an epoxy resin having a tetrakis (hydroxyphenyl) ethane structure, an epoxy resin having an aminophenol structure, and a bis (aminophenyl) methane structure.
- An epoxy resin can be mentioned. Among them, an epoxy resin having a bis (aminophenyl) methane structure is preferable, and examples thereof include N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane and the like.
- the epoxy resin which has a 3 or more glycidyl ether group is preferable from a viewpoint of the storage stability of an adhesive composition.
- the epoxy resin forms a crosslinked structure, and the heat resistance of the pressure-sensitive adhesive under a high-temperature solution is improved.
- self-organization using an epoxy resin as a matrix occurs due to cross-linking, and as a result, a sea-island structure is locally formed.
- Such a sea-island structure is considered to provide toughness to the cured adhesive.
- Such a trifunctional or higher functional epoxy resin can be contained within a range that does not impair the effects of the present invention, and when the trifunctional or higher functional epoxy resin is included, its content is based on the total mass of the pressure-sensitive adhesive composition. 5 to 50% by mass.
- a commercially available epoxy resin may be used as the trifunctional or higher functional epoxy resin.
- jER1032H60 epoxy resin having a tris (hydroxyphenyl) methane structure
- jER1031S tetrakis (manufactured by Mitsubishi Chemical Corporation)
- Hydroxyphenyl) epoxy resin having ethane structure Daicel Corporation EHPE3150 (epoxy resin having oxysilanylcyclohexane structure), Mitsubishi Chemical Corporation jER630 (epoxy resin having aminophenol structure), Mitsubishi Chemical Corporation jER604 (Epoxy resin having a diaminodiphenylmethane structure) and the like.
- the above trifunctional or higher functional epoxy resins may be used alone or in appropriate combination of two or more.
- the content of epoxy resin including bisphenol A type epoxy resin and bisphenol A type epoxy resin which is liquid at room temperature and can be contained as needed, trifunctional epoxy resin, etc. is the resin in the adhesive composition. It is preferable that it is the range of 40 mass parts or more and 90 mass parts or less with respect to the total amount of a component.
- the epoxy-modified silicone resin may be contained in the pressure-sensitive adhesive composition as necessary. By including an epoxy-modified silicone resin, both heat resistance and flexibility (toughness) can be achieved.
- the epoxy-modified silicone resin refers to a silicone resin in which an epoxy group or an epoxy compound is introduced.
- the silicone resin is a compound having a polyorganosiloxane skeleton, and is usually a compound having a main skeleton (main chain) portion mainly composed of repeating organosiloxane units, and the main skeleton having at least one silanol group.
- An epoxy-modified silicone resin can be obtained by an addition reaction between a group and an epoxy compound.
- the main skeleton of the silicone resin may have a branched structure as long as it has at least one silanol group.
- the reaction material of an epoxy resin and a silicone resin may be sufficient, for example, the thing by which OH group and silanol in an epoxy resin frame
- the epoxy-modified silicone resin is used.
- Epoxy-modified silicone resins may be used alone or in appropriate combination of two or more.
- an epoxy-modified silane compound may be used in combination.
- an epoxy-modified silicone resin and an epoxy-modified silane compound in combination, water resistance and adhesive strength are further improved.
- the epoxy-modified silane compound include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, ( ⁇ -glycidoxypropyl) (methyl) dimethoxysilane, ( ⁇ -glycidoxypropyl) (ethyl) dimethoxysilane, ( ⁇ -glycidoxypropyl) (methyl) Diethoxysilane, ( ⁇ -glycidoxypropyl) (ethyl) diethoxysilane
- epoxy-modified compounds may be used alone or in combination of two or more. Moreover, you may use a commercially available thing, for example, ES1001N, ES1002T, ES1023 (above, the Shin-Etsu Silicone company make);
- the content is 5 parts by mass or more and 40 masses with respect to the total amount of the resin components (that is, epoxy resin, epoxy-modified silicone resin and acrylic particles) in the pressure-sensitive adhesive composition. It is preferable that it is the range below a part.
- the acrylic resin is included in the pressure-sensitive adhesive composition as necessary, but is preferably included.
- a methyl methacrylate-butyl acrylate-methyl methacrylate binary copolymer (including a polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate binary copolymer) or a modified product thereof is used.
- a binary block copolymer comprising such a methacrylic acid ester polymer block (hereinafter sometimes abbreviated as MMA) and a butyl acrylate polymer block (hereinafter sometimes abbreviated as BA),
- MMA methacrylic acid ester polymer block
- BA butyl acrylate polymer block
- the obtained pressure-sensitive adhesive layer has toughness and has excellent adhesive strength in the usage environment for vehicle body applications.
- a pressure-sensitive adhesive layer that can be held and has excellent adhesive strength holding characteristics can be realized.
- epoxy resin simply refers to both the case of a bisphenol A type epoxy resin and the case of containing a bisphenol A type epoxy resin and a tri- or higher functional epoxy resin.
- the MMA portion becomes a “hard” segment and the BA portion becomes a “soft” segment.
- an acrylic resin has been added in order to impart toughness (flexibility) to the epoxy resin, but the heat resistance of the pressure-sensitive adhesive itself has been reduced by adding the acrylic resin. It was. If the acrylic resin has both a “hard” segment and a “soft” segment as described above, the “hard” segment part contributes to heat resistance, and the “soft” segment part contributes to toughness or flexibility. It is considered that a pressure-sensitive adhesive layer having toughness and capable of maintaining excellent adhesive strength in an environment for use in vehicle bodies can be realized.
- the MMA-BA-MMA binary copolymer may be a modified product in which a functional group such as a carboxylic acid, a hydroxyl group or an amide group is introduced into a part of the BA block or MMA block.
- a functional group such as a carboxylic acid, a hydroxyl group or an amide group
- the MMA-BA-MMA binary copolymer When the MMA-BA-MMA binary copolymer is added to the epoxy resin, the MMA block part is compatible with the epoxy resin, and the BA block part is not compatible with the epoxy resin, so that self-assembly using the epoxy resin as a matrix occurs. . As a result, a sea-island structure in which the epoxy resin is the sea and the acrylic resin is the island appears before the resin is cured. In addition, when the functional group as described above is introduced into the MMA-BA-MMA binary copolymer, the compatibility between the epoxy resin and the acrylic resin is improved, so that the island portion is reduced, and both are apparently It becomes a compatible state.
- an epoxy resin and an acrylic resin MMA-BA-MMA binary copolymer
- MMA-BA-MMA binary copolymer MMA-BA-MMA binary copolymer
- the acrylic resin (island) is dispersed in the form of fine particles of nano-order level in the epoxy resin (sea) before the resin is cured, and an apparent compatibility state is expressed. Excellent adhesive strength can be maintained by curing the resin while maintaining an apparent compatible state.
- the acrylic particles have a core-shell structure having butadiene rubber and polymethacrylate or polyacrylate.
- the butadiene rubber-only particles When the butadiene rubber-only particles are added to the epoxy resin, the butadiene rubber-only particles may usually aggregate in the pressure-sensitive adhesive composition or the pressure-sensitive adhesive layer.
- the acrylic fine particles having the core-shell structure of the present invention since the butadiene rubber is covered with polymethacrylate or polyacrylate, it is difficult to aggregate even if added to the epoxy resin, and the butadiene rubber in the core portion of the acrylic particles. Can be dispersed in the state of particles while building a network of acrylic particles in the pressure-sensitive adhesive composition or in the pressure-sensitive adhesive layer, and toughness can be imparted to the obtained pressure-sensitive adhesive layer.
- the acrylic particles preferably have a reactive functional group.
- the reactive functional group is preferably an epoxy group. It is preferable to have a reactive functional group such as an epoxy group in the polymethacrylate or polyacrylate of the shell portion. Or it is good also considering the polymethacrylate or polyacrylate of a shell part as an epoxy modified polymethacrylate or an epoxy modified polyacrylate beforehand.
- the epoxy-modified polymethacrylate or the epoxy-modified polyacrylate is not particularly limited as long as an epoxy group is introduced into the polymethacrylate or polyacrylate. For example, an epoxy group is introduced by reacting an acrylic chain of glycidyl methacrylates. It may be a thing.
- the acrylic particles preferably have an average particle size of 200 nm or less.
- acrylic fine particles having an average particle size of, for example, ⁇ order the Tg of the acrylic portion constituting the fine particles becomes remarkable, so that the Tg apparently decreases.
- acrylic particles having an average particle size of 200 nm or less behave as if the acrylic particles dispersed in the pressure-sensitive adhesive composition are compatible with each other, so that the Tg of the acrylic part is hidden. Therefore, the Tg is not lowered as a whole, but rather a network of acrylic fine particles is formed locally, so that the Tg is improved.
- a reactive functional group such as an epoxy group is introduced into acrylic particles, the effect of improving Tg is remarkable.
- the improvement in Tg greatly affects the water resistance, and the water resistance can be maintained by keeping the Tg high.
- the lower limit of the average particle size of the acrylic fine particles is not particularly limited, but is preferably 10 nm or more from the viewpoints of availability, toughness imparting effect, reaggregation property, and the like.
- the acrylic particles are preferably contained so that the mass ratio of the acrylic particles is 3% or more and 33% or less when the total mass of the pressure-sensitive adhesive composition is 100%. Further, the ratio (M1 / M2) between the content M1 of the acrylic particles and the content M2 of the epoxy resin (including a bisphenol A type epoxy resin and also including a trifunctional or higher functional epoxy resin as necessary) is 0. It is preferably included so as to be 05 or more and 0.35 or less.
- acrylic particles are dispersed in nano-order level in the epoxy resin (sea) before curing the resin, and apparent compatibility.
- a condition is developed. Excellent adhesive strength can be maintained by curing the resin while maintaining an apparent compatible state.
- the inclusion of acrylic particles facilitates localization so that the acrylic particles are finely dispersed in the island structure of the sea island.
- the special sea-island structure in which acrylic particles are finely dispersed in the island part of the sea-island structure can increase the water resistance of the obtained adhesive layer, especially in the case where it is used for a car body, such as vibration, impact, outside temperature. Even when exposed to severe factors such as contact with wind, rain, water or snow melting agent, it is possible to bond with higher strength at the time of bonding, and higher strength can be maintained over time.
- (Curing agent) An epoxy resin, an acrylic resin, and a curing agent (including a curing catalyst) undergo a reaction by heating or the like to cure the pressure-sensitive adhesive composition.
- curing agent is contained in an adhesive composition.
- the curing agent examples include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), diaminodiphenylsulfone ( Aromatic polyamines such as DDS); amine curing agents such as polyamine compounds including dicyandiamide (DICY) and organic acid dihydralazide; and alicyclic acids such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) Examples of anhydrides (liquid acid anhydrides); trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), aromatic acid anhydrides such as benzophenone tetracarboxylic acid (BTDA), etc .; be able to.
- DETA diethylenetriamine
- TETA triethylenet
- isocyanate type hardening agents such as phenol type hardening
- curing agents such as a phenol resin, and block isocyanate, etc.
- isocyanate type hardening agents such as phenol type hardening
- curing agents such as a phenol resin, and block isocyanate, etc.
- amine-based curing agents can be suitably used, and dicyandiamide-based curing agents are particularly preferable.
- a dicyandiamide type curing agent When a dicyandiamide type curing agent is used as the curing agent, it is preferable to use a block isocyanate in combination. By using dicyandiamide and blocked isocyanate in combination, the storage stability of the pressure-sensitive adhesive is improved.
- a hydroxyl group is present on the surface of a lightweight metal such as aluminum or magnesium that is preferably used for a vehicle body by using a cyanate curing agent in combination, a crosslink is formed between the hydroxyl group and the adhesive component. Adhesion improves.
- Blocked isocyanate is a reaction product obtained by addition reaction of a blocking agent to the isocyanate group of the isocyanate compound. Accordingly, the blocked isocyanate is one in which the isocyanate group is protected by the blocking agent and inactivated. By heating the blocked isocyanate at a predetermined temperature, the blocking agent is dissociated from the isocyanate group, that is, deblocked, and an active isocyanate group is regenerated.
- isocyanate compound examples include isocyanates having two or more isocyanate groups in one molecule.
- aliphatic isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate, 4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate and Examples thereof include aromatic isocyanates such as 4,4-diphenyl diisocyanate, and alicyclic isocyanates such as dicycloheptane triisocyanate.
- the blocking agent examples include active methylene blocking agents such as ethyl acetoacetate, phenol blocking agents such as phenol, cresol and xylenol, pyrazole blocking agents such as dimethylpyrazole, methanol, ethanol, diethyl malonate, methyl lactate and Alcohol block agents such as ethyl lactate, oxime block agents such as methyl ethyl ketone oxime, diacetyl monooxime and cyclohexane oxime, mercaptan block agents such as butyl mercaptan, t-butyl mercaptan and thiophenol, and imide blocks such as succinimide Agents, amine blocking agents such as aniline and butylamine, imidazole blocking agents such as imidazole and 2-ethylimidazole, and methyleneimine and propyleneimine Imine blocking agents like can be given.
- active methylene blocking agents such as ethyl
- block isocyanate may be used, and examples thereof include MF-K60B, SBN-70D, TPA-B80E, 17B-60PX, E402-B80B, and E402-B80T (manufactured by Asahi Kasei Chemicals Corporation).
- the content of the curing agent in the pressure-sensitive adhesive composition can be appropriately determined depending on the amine value or acid value of the curing agent.
- the content of the curing agent is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin and the epoxy-modified silicone resin. If the compounding ratio of the curing agent is within this range, the heat resistance after bonding can be increased, the adhesive strength can be prevented from deteriorating due to temperature change, and the storage stability (pot life) can be maintained. If the storage stability is low, the curing reaction may proceed during the storage period when the adhesive sheet is stored until it is bonded to the adherend. When there is too much content of a hardening
- the pressure-sensitive adhesive composition according to the present invention for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipping properties, mold release properties, flame retardancy, for the purpose of improving and modifying antifungal properties, electrical properties, strength, etc., for example, lubricants, plasticizers, fillers, fillers, antistatic agents, antiblocking agents, crosslinking agents, antioxidants, UV absorption A colorant such as an agent, a light stabilizer, a dye, and a pigment, and the like may be added. Further, a silane-based, titanium-based, aluminum-based or other coupling agent can be further included as necessary. Thereby, the adhesiveness between the resin, the adherend, and the resin and the core material to be described later can be improved.
- the pressure-sensitive adhesive composition can be prepared by mixing the above-described components and kneading and dispersing as necessary.
- the mixing or dispersing method is not particularly limited, and is an ordinary kneading and dispersing machine such as a two-roll mill, a three-roll mill, a pebble mill, a tron mill, a Szegvari attritor, a high-speed impeller disperser, a high-speed stone mill, A high speed impact mill, a desper, a high speed mixer, a ribbon blender, a kneader, an intensive mixer, a tumbler, a blender, a desperser, a homogenizer, an ultrasonic disperser, and the like can be applied.
- mix and stir these mix and stir these first, then stir the curing agent, dilute with a solvent, mix and stir the soft epoxy resin, then mix and stir the acrylic resin It is preferable to do.
- the pressure-sensitive adhesive sheet 10 has a pressure-sensitive adhesive layer 1 between a first release film 2A and a second release film 2B.
- the adhesive layer 1 is a core-shell structure that includes at least a bisphenol A type epoxy resin, acrylic particles, and a curing agent, and the acrylic particles include butadiene rubber and polymethacrylate or polyacrylate.
- the adhesive layer 1 is bonded to the metal and the composite resin through the adhesive layer 1 and then 200 ° C. in each of 80 ° C. water, 80 ° C. 10% NaCl solution, and 80 ° C. 50% CaCl 2 solution.
- the adhesive strength retention after the immersion for a time satisfies 68% or more.
- the first release film 2A and the second release film 2B may be collectively referred to as the release film 2.
- the adhesive layer 1 may further include a core material (not shown), and the core material may be impregnated with the adhesive material.
- a core material a woven fabric or a nonwoven fabric is preferable, and various conventionally known woven fabrics or nonwoven fabrics can be exemplified.
- heat-resistant plastic fibers such as liquid crystal polymers, glass fibers, aramid fibers, carbon fibers, polyester nonwoven fabrics, vinylon fibers, urethane foam, etc. can be used, and woven fabrics and nonwoven fabrics composed of these are used. Can do.
- the core material is coated with the pressure-sensitive adhesive composition on the surface of the core material by running the first release film 2A and the core material by using a coating machine.
- the pressure-sensitive adhesive sheet 10 can be obtained by drying the impregnated material and bonding the second release film 2B to the coated surface.
- the method for applying the pressure-sensitive adhesive composition to the release film 2 is not particularly limited.
- the pressure-sensitive adhesive composition is applied to the release surface of the first release film 2A or the core material surface obtained by superimposing the first release film 2A and the core material by the above-described coating method, and then dried. What is necessary is just to bond the release film 2B together.
- the viscosity of the pressure-sensitive adhesive composition (coating solution) is adjusted to about 1 to 20000 centistokes (25 ° C.), preferably 1 to 2000 centistokes. When impregnating and applying to the core material, it is preferable that the viscosity is low, and it is 1 to 1000 centistokes.
- the first release film 2A and the second release film 2B may be the same or different.
- the release film 2 conventionally known ones such as a release film, a separate paper, a separate film, a separate paper, a release film, and a release paper can be suitably used.
- the release layer is not particularly limited as long as it has a releasability.
- the release layer is formed by applying a coating liquid in which the release layer component is dispersed and / or dissolved on one side of the base film for the release film, followed by heating and drying and / or curing.
- a coating method of the coating liquid a known and arbitrary coating method can be applied, for example, roll coating, gravure coating, spray coating or the like.
- the peel strength of the first and second release films is preferably about 1 to 2000 mN / cm, more preferably 100 to 1000 mN / cm, with respect to the pressure-sensitive adhesive sheet.
- the release force of the release layer is less than 1 mN / cm, the release force from the pressure-sensitive adhesive sheet or the adherend is weak, and it peels off or partially floats.
- the peeling force of a release layer is strong and it is hard to peel.
- addition and / or polycondensation-type curable silicone resins for release paper which are mainly composed of polydimethylsiloxane, are preferred.
- the exposed adhesive layer 1 is sandwiched between two identical or different first adherends and second adherends and held with the adhesiveness of the adhesive layer 1.
- the pressure-sensitive adhesive layer 1 can be cured by heating or pressure heating, and the first adherend and the second adherend can be firmly bonded.
- the adherends can be temporarily fixed using the initial adhesiveness, and then the adherend can be bonded by thermosetting the adhesive sheet 10 by, for example, a batch method, so that steps such as preheating are omitted. And productivity is significantly improved.
- the adherend is not particularly limited, but a light weight composite resin such as aluminum or magnesium used for the vehicle body and FRP (CFRP: Carbon Fiber Reinforced Plastics, GFRP: Glass Fiber Reinforced Plastics). And can be preferably used for adhesion between the lightweight metal and the lightweight composite resin.
- a metal, an inorganic material, an organic material, a composite material combining these, a laminated material, or the like may be used.
- the heating temperature at the time of curing is about 60 ° C to 250 ° C, preferably 100 ° C to 180 ° C.
- the heating time is 1 to 240 minutes, preferably 10 to 120 minutes.
- the pressure-sensitive adhesive layer 1 of the cured pressure-sensitive adhesive sheet 10 has initial pressure-sensitive adhesiveness, does not have a preheating process, and can work while holding the adherend only with pressure-sensitive adhesive force. Therefore, the workability is good and the cost is low.
- the pressure-sensitive adhesive layer 1 formed of the pressure-sensitive adhesive composition according to the present invention after bonding such metal and composite resin, water at 80 ° C., 10% NaCl solution at 80 ° C., And the adhesive strength retention after satisfying each of the 50% CaCl 2 solution at 80 ° C. for 200 hours satisfies 68% or more.
- the bonding body of metals such as aluminum and iron
- the bonding body of FRP and CFRP can be obtained.
- These bonded bodies can maintain excellent adhesive strength without being affected by temperature changes, have low brittleness, have excellent shear strength, high impact resistance, and heat resistance.
- it can be preferably applied to applications that are exposed to severe factors such as vibration, impact, changes in outside air temperature, wind and rain, contact with water and snow melting agents, and the like. If it is such an application, it is not limited to automobiles, and not only in the fields of aircraft, ships, etc., but also in the fields of electronic equipment, electronic equipment casings, home appliances, infrastructure structures, lifeline building materials, general building materials, etc. Can be used.
- each composition of each layer is the mass part of solid content except a solvent.
- Example 1 The pressure-sensitive adhesive composition of Example 1 was prepared by mixing a bifunctional bisphenol A type epoxy resin (JER1001, Mitsubishi Chemical Corporation) with acrylic particles having a core-shell structure in which the shell part is polymethacrylate and the core part is butadiene rubber.
- a bifunctional bisphenol A type epoxy resin JER1001, Mitsubishi Chemical Corporation
- Example 2 The pressure-sensitive adhesive composition of Example 2 was prepared by mixing a bifunctional bisphenol A type epoxy resin (JER1001, Mitsubishi Chemical Corporation) with acrylic particles having a core-shell structure in which the shell part is polymethacrylate and the core part is butadiene rubber. The composition was adjusted with 150 parts by mass of the composition formulated at a mass ratio of 67:33, 14 parts by mass of dicyandiamide (DICY7, Mitsubishi Chemical Corporation), and 9 parts by mass of imidazole (ajicure MYH, Ajinomoto Fine Techno Co., Ltd.).
- a core material (polyester nonwoven fabric: OL150S, Nippon Bayline) in which the pressure-sensitive adhesive compositions obtained in Examples 1 and 2 and Comparative Example 1 were superimposed on a release film (separator film: SP-PET 03BU, manufactured by Tosero Co., Ltd.) Applied to the surface of the product by a comma coater so that the coating amount was 100 g / m 2, and the core material was impregnated with an adhesive to form an adhesive layer.
- a release film (separator film: SP-PET 01BU, manufactured by Tosero Co., Ltd.) was bonded to prepare an adhesive sheet in which the release sheets were bonded to both sides of the adhesive layer.
- the produced adhesive sheet was cut into a length of 25 mm and a width of 12.5 mm, and one release film was peeled off to expose the adhesive layer.
- the exposed adhesive layer was affixed to the tip of aluminum (JIS standard: 6061 alloy, length 100 mm, width 25 mm, thickness 1.5 mm).
- the other release film was peeled off from the adhesive sheet affixed to the aluminum to expose the adhesive layer.
- An uncured CFRP prepreg (TR3110 # 331, manufactured by Mitsubishi Rayon Co., Ltd.) from which the release film has been removed is attached to the exposed adhesive layer, and an adhesive sheet from which the release film has been released is attached to the exposed adhesive layer.
- the exposed adhesive layer was affixed to the aluminum tip.
- the final configuration was aluminum / adhesive layer / prepreg layer / adhesive layer / aluminum.
- a pressure sensitive adhesive was applied to a release film (separator film: SP-PET 01BU, manufactured by Tosero Co., Ltd.) with a comma coater so that the coating amount after drying was 50 g / m 2, and dried at 100 ° C. for 3 minutes. The appearance of the coated surface was observed. Evaluation criteria were “ ⁇ ”: when the coating film had a uniform thickness ( ⁇ 5 ⁇ m), and “ ⁇ ”: when the adhesive film was repelled on the surface of the release film and there was an uncoated part. . The results are shown in Table 1.
- Example 1 it was confirmed that the structure is a sea-island structure in which nano-sized acrylic particles are locally scattered. The sea seems to be epoxy resin and the small islands are acrylic particles.
- Example 1 an acrylic resin is added, but in FIGS. 2A and 3A, a sea-island structure due to the acrylic resin is observed due to an apparent compatibility state. It seems not.
- Example 1 has a higher softening point than the adhesive layer of Comparative Example 1. It was. From this result, it can be seen that the pressure-sensitive adhesive layer produced from the pressure-sensitive adhesive composition obtained in Example 1 can maintain excellent adhesive strength even in a high-temperature hot water environment.
- FIG. 5 is a graph (A) of storage elastic modulus (E ′) at the initial stage and after 80 hours at 80 ° C., and loss tangent (at the initial stage and after 200 hours at 80 ° C.) for the adhesive layer obtained in Example 1.
- 6 is a graph (B) of the temperature dependence of tan ⁇ .
- FIG. 6 is a graph (A) of the storage elastic modulus (E ′) at the initial time and after 80 hours at 80 ° C. with respect to the adhesive layer obtained in Comparative Example 1. And (B) of the temperature dependence of the loss tangent (tan ⁇ ) at the initial time and after 80 hours at 80 ° C.
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Abstract
Description
本発明に係る粘着剤組成物は、粘着層を形成できる粘着剤組成物である。そして、その粘着剤組成物は、エポキシ樹脂とアクリル粒子と硬化剤とを少なくとも含み、そのアクリル粒子がブタジエン系ゴムとポリメタクリレート又はポリアクリレートとを有するコアシェル構造体である。
本発明の粘着剤組成物に含まれるエポキシ樹脂は、少なくとも1つ以上のエポキシ基またはグリシジル基を有するプレポリマーであり、硬化剤との併用により架橋重合反応により硬化して、硬化後の粘着剤組成物の耐熱性を向上させることができる。エポキシ樹脂としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂等のビスフェノール型エポキシ樹脂、ノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂等のノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂等のエポキシ樹脂等の芳香族系または脂環式のエポキシ樹脂や、脂肪族系のエポキシ樹脂、さらには、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールAノボラック樹脂等のノボラック型フェノール樹脂、レゾールフェノール樹脂等のフェノール樹脂、ユリア(尿素)樹脂、メラミン樹脂等のトリアジン環を有する樹脂、不飽和ポリエステル樹脂、ビスマレイミド樹脂、ポリウレタン樹脂、ジアリルフタレート樹脂、シリコン樹脂、ベンゾオキサジン環を有する樹脂、シアネートエステル樹脂等が挙げられる。これらエポキシ系樹脂の中でも、ビスフェノール骨格を有する剛直な2官能エポキシ樹脂であるビスフェノールA型エポキシ樹脂を好適に使用できる。ビスフェノールA型エポキシ樹脂には、ビスフェノール骨格の繰り返し単位数によって、主鎖が0~1のビスフェノールA型エポキシ樹脂は常温で液体であり、主鎖が2~10のビスフェノールA型エポキシ樹脂は常温で固体である。本発明では、常温で固体のビスフェノールA型エポキシ樹脂を用いることが好ましい。
エポキシ変性シリコーン樹脂は、必要に応じて粘着剤組成物に含まれていてもよい。エポキシ変性シリコーン樹脂が含まれることにより、耐熱性と柔軟性(靱性)を両立させることができる。エポキシ変性シリコーン樹脂は、シリコーン樹脂の一部にエポキシ基又はエポキシ化合物を導入したものをいう。シリコーン樹脂は、ポリオルガノシロキサン骨格を有する化合物であり、通常、主骨格(主鎖)部分が主としてオルガノシロキサン単位の繰り返しからなり、その主骨格が少なくとも1つのシラノール基を備える化合物であり、このシラノール基とエポキシ化合物との付加反応によりエポキシ変性シリコーン樹脂を得ることができる。シリコーン樹脂の主骨格は、少なくとも1つのシラノール基を有していれば分枝状の構造を有するものであってもよい。また、エポキシ樹脂とシリコーン樹脂との反応物であってもよく、例えばエポキシ樹脂骨格中のOH基とシラノールとが反応したものであってもよい。なお、当該反応物において、エポキシ樹脂の方が多くなり見かけ上エポキシ樹脂にシリコーンがぶら下がっているようなものであっても、エポキシ変性シリコーン樹脂とする。エポキシ変性シリコーン樹脂は単独で又は2種以上を適宜組み合わせて使用してもよい。
アクリル樹脂は、粘着剤組成物に必要に応じて含まれるが、含まれていることが好ましい。アクリル樹脂として、メチルメタクリレート-ブチルアクリレート-メチルメタクリレートの2元共重合体(ポリメチルメタクリレート-ポリブチルアクリレート-ポリメチルメタクリレートの2元共重合体を含む)又はその変性物を使用する。このようなメタアクリル酸エステル重合体ブロック(以下、MMAと略すことがある。)と、アクリル酸ブチル重合体ブロック(以下、BAと略すことがある)とからなる2元ブロック共重合体を、上記したビスフェノールA型エポキシ樹脂や3官能以上のエポキシ樹脂を含むエポキシ樹脂に添加することにより、得られた粘着層は靱性を有し、かつ車体用途での使用環境下において、優れた接着強度を保持でき、かつ接着強度保持特性にも優れる粘着層を実現できる。以下において、単に「エポキシ樹脂」というときは、ビスフェノールA型エポキシ樹脂の場合と、ビスフェノールA型エポキシ樹脂と3官能以上のエポキシ樹脂とを含む場合の両方をいう。
アクリル粒子は、ブタジエン系ゴムとポリメタクリレート又はポリアクリレートとを有するコアシェル構造体を有している。ブタジエン系ゴムのみの粒子をエポキシ樹脂に添加した場合、通常、ブタジエン系ゴムのみの粒子は粘着剤組成物中や粘着層中で凝集してしまうおそれがある。それに対して、本発明のコアシェル構造のアクリル微粒子では、ブタジエン系ゴムがポリメタクリレート又はポリアクリレートに覆われているので、エポキシ樹脂に添加しても凝集しにくく、アクリル粒子のコア部のブタジエン系ゴムを粘着剤組成物中や粘着層中でアクリル粒子群のネットワークを構築させながら粒子の状態で分散させることができ、得られた粘着層に靱性を付与することができる。
エポキシ樹脂、アクリル樹脂及び硬化剤(硬化触媒を含む)は、加熱等により反応が進行して粘着剤組成物が硬化する。本発明においては、硬化反応を促進するために、粘着剤組成物中に硬化剤が含まれる。硬化剤としては、例えばジエチレントリアミン(DETA)、トリエチレンテトラミン(TETA)、メタキシレリレンジアミン(MXDA)等の脂肪族ポリアミン、ジアミノジフェニルメタン(DDM)、m-フェニレンジアミン(MPDA)、ジアミノジフェニルスルホン(DDS)等の芳香族ポリアミン;ジシアンジアミド(DICY)、有機酸ジヒドララジド等を含むポリアミン化合物等のアミン系硬化剤;ヘキサヒドロ無水フタル酸(HHPA)、メチルテトラヒドロ無水フタル酸(MTHPA)等の脂環族酸無水物(液状酸無水物);無水トリメリット酸(TMA)、無水ピロメリット酸(PMDA)、ベンゾフェノンテトラカルボン酸(BTDA)等の芳香族酸無水物等;の酸無水物系硬化剤を挙げることができる。また、フェノール樹脂等のフェノール系硬化剤、ブロックイソシアネート等のイソシアネート系硬化剤等も挙げることができる。これらの中でも、アミン系硬化剤を好適に使用することができ、特にジシアンジアミド系硬化剤が好ましい。
本発明に係る粘着剤組成物には、必要に応じて、例えば、加工性、耐熱性、耐候性、機械的性質、寸法安定性、抗酸化性、滑り性、離形性、難燃性、抗カビ性、電気的特性、強度、その他等を改良、改質する目的で、例えば、滑剤、可塑剤、充填剤、フィラー、帯電防止剤、アンチブロッキング剤、架橋剤、酸化防止剤、紫外線吸収剤、光安定剤、染料、顔料等の着色剤、その他等を添加してもよい。また、必要に応じて、さらにシラン系、チタン系、アルミニウム系等のカップリング剤を含むことができる。これにより樹脂と被着体及び樹脂と後述する芯材財との密着性を向上させることができる。
本発明に係る粘着シート10は、図1に示すように、粘着層1を、第1離型フィルム2Aと第2離型フィルム2Bとの間に有している。その粘着層1は、ビスフェノールA型エポキシ樹脂とアクリル粒子と硬化剤とを少なくとも含み、そのアクリル粒子が、ブタジエン系ゴムとポリメタクリレート又はポリアクリレートとを有するコアシェル構造体である。また、その粘着層1は、粘着層1を介して金属と複合樹脂とを接着した後、80℃の水、80℃の10%NaCl溶液、及び80℃の50%CaCl2溶液のそれぞれに200時間浸漬させた後における接着強度保持率が68%以上を満たすものである。なお、以下では、第1離型フィルム2Aと第2離型フィルム2Bとを合わせて離型フィルム2ということがある。
被着体との接合は、粘着シート10の第1離型フィルム2A及び第2離型フィルム2Bを剥離して除去し、粘着層1を露出させる。露出した粘着層1を、2つの同じ又は異なる第1被着体及び第2被着体で挟み、粘着層1の粘着性で保持させる。次いで、加熱、又は加圧加熱することで粘着層1を硬化させて、第1被着体及び第2被着体を強固に接着させることができる。このように、初期粘着性を利用して、被着体同士を仮固定でき、その後に、例えばバッチ方式により粘着シート10を熱硬化させて被着体を接着できるため、プレヒート等の工程を省くことができるとともに、生産性が著しく向上する。
本発明に係る粘着シート10を用いることにより、従来の溶接法では困難な、ガラス繊維や炭素繊維のFRPと、アルミニウムやマグネシウム等の軽量金属とを強力に接合できる。本発明に係る粘着剤組成物で形成された粘着層1は、後述する実施例に示すように、そうした金属と複合樹脂とを接着した後、80℃の水、80℃の10%NaCl溶液、及び80℃の50%CaCl2溶液のそれぞれに200時間浸漬させた後における接着強度保持率が68%以上を満たす。
実施例1の粘着剤組成物を、2官能のビスフェノールA型エポキシ樹脂(JER1001、三菱化学株式会社)と、シェル部がポリメタクリレートでコア部がブタジエン系ゴムであるコアシェル構造を有するアクリル粒子とを、質量基準で67:33の割合で配合した組成物65質量部、4官能のエポキシ樹脂(JER604、テトラグリシジルジアミノジフェニルメタン、三菱化学株式会社)65質量部、シリコーン骨格エポキシ樹脂(ES1023、信越化学工業株式会社)20質量部、アクリル樹脂(M22N、PMMA-PBA-PMMA共重合体、アルケマ株式会社)30質量部、エポキシ型シランカップリング剤(KBM403、信越化学工業株式会社)2質量部、ジシアンジアミド(DICY7、三菱化学株式会社)14質量部、イミダゾール(ajicureMYH、味の素ファインテクノ株式会社)9質量部、で調製した。
実施例2の粘着剤組成物を、2官能のビスフェノールA型エポキシ樹脂(JER1001、三菱化学株式会社)と、シェル部がポリメタクリレートでコア部がブタジエン系ゴムであるコアシェル構造を有するアクリル粒子とを、質量基準で67:33の割合で配合した組成物150質量部、ジシアンジアミド(DICY7、三菱化学株式会社)14質量部、イミダゾール(ajicureMYH、味の素ファインテクノ株式会社)9質量部で、調整した。
比較例1の粘着剤組成物を、2官能のビスフェノールA型エポキシ樹脂(JER828、三菱化学株式会社)200質量部、ジシアンジアミド(DICY7、三菱化学株式会社)14質量部、イミダゾール(ajicureMYH、味の素ファインテクノ株式会社)9質量部で調製した。
実施例1,2と比較例1で得られた粘着剤組成物を、離型フィルム(セパフィルム:SP-PET 03BU、東セロ株式会社製)に重ね合わせた芯材(ポリエステル不織布:OL150S、日本バイリーン株式会社製)の表面に、コンマコーターにて塗布量が100g/m2となるように塗布し、芯材に粘着剤を含浸させて粘着層を形成した。その粘着層上に、離型フィルム(セパフィルム:SP-PET 01BU、東セロ株式会社製)を貼り合わせることにより、粘着層の両面に離型シートが貼り合わされた粘着シートを作製した。
作製された粘着シートを、長さ25mm、幅12.5mmに裁断し、一方の離型フィルムを剥離して粘着層を露出させた。露出した粘着層をアルミニウム(JIS規格:6061合金、長さ100mm、幅25mm、厚さ1.5mm)の先端部分に貼り付けた。アルミニウムに貼りつけた粘着シートから他方の離型フィルムを剥離して粘着層を露出させた。露出した粘着層に、剥離フィルムを除去した未硬化CFRPプリプレグ(TR3110#331、三菱レイヨン株式会社製)を貼り付け、さらにその上に上記と同様に離形フィルムを剥離した粘着シートを貼りつけ、露出した粘着層をアルミニウムの先端部分に貼りつけた。最終構成としては、アルミニウム/粘着層/プリプレグ層/粘着層/アルミニウムとした。
(初期の接着強度)
作製された貼合体の両端を、23℃、50%RHの環境下でテンシロン万能材料試験機(RTF-1350、株式会社エーアンドデイ製)に固定し、10mm/分で引っ張り、せん断強度を測定した。測定結果を表1に示した。
作製された貼合体を蒸留水中に浸漬し、80℃の環境下に200時間静置した後、蒸留水中から貼合体を取り出し、23℃、50%RHの環境下に24時間静置した。続いて、上記と同様にしてせん断強度を測定した。また、初期の粘着強度に対する高温熱水環境下に保管した後の接着強度の保持率を、[高温熱水環境下に保管した後の接着強度(MPa)]/[初期粘着強度(MPa)]×100(%)、として算出した。結果を表1に示した。
離型フィルム(セパフィルム:SP-PET 01BU、東セロ株式会社製)に、乾燥後の塗布量が50g/m2となるように粘着剤をコンマコーターにて塗布し、100℃で3分間の乾燥を行い、塗布面の外観を観察した。評価基準は、「○」:塗布膜が均一な厚さ(±5μm)であるとき、「×」:離型フィルムの表面で粘着剤が弾いて塗布されていない箇所が存在したとき、とした。結果を表1に示した。
作製された粘着シートを用い、各粘着シートから一方の離型フィルムを剥離して粘着層を露出させ、剥離した粘着層の部分に、表面を洗浄したアルミニウム板(JIS規格:6061合金、長さ100mm、幅25mm、厚さ1.5mm)を載置し、その上から、手動式圧着装置(JIS Z 0237)を用いて圧着速度約5mm/秒で1往復させて、粘着シートとアルミニウム板とを貼り合わせて試験サンプルを得た。次いで、得られた試験サンプルを、テンシロン万能試験機(株式会社オリエンテック製:RTA-1T)を用いて、180°、300mm/分でピール引き剥がし強度(N/cm)を測定した。また、作製された粘着シートを、23℃、50%RHの環境下に1月間静置した後、上記と同様にして試験サンプルを作製し、ピール引き剥がし強度を測定した。試験サンプルを作製した後の初期粘着力に対して、1月間静置下した後であっても50%以上の粘着力を保持しているものを「○」とし、50%未満のものを「×」とした。結果を表1に示した。
実施例1,2及び比較例1で得られた粘着剤組成物で作製した粘着シートを、130℃で2時間硬化させた後、一方の離型フィルムを剥離して粘着層を露出させ、電子顕微鏡(製品名:SU3500、日立ハイテク株式会社製)を用いて表面観察を行い、粘着剤の相溶状態を確認した。また、同様にして透過型電子顕微鏡(TEM)を用いて観察した。得られた電子顕微鏡写真を図2に、透過型顕微鏡写真を図3に示した。図2(A)及び図3(A)に示すように、実施例1,2の粘着剤組成物で得た粘着層は、海島構造が発現していることが観察された。ナノサイズのアクリル粒子が局所的に点在している海島構造となっていることが確認された。海はエポキシ樹脂、小さい島はアクリル粒子であると思われる。なお、実施例1では、アクリル樹脂が添加されているが、図2(A)及び図3(A)では、見かけ上の相溶状態のために、アクリル樹脂に起因する海島構造は観察されていないと思われる。
実施例1,2及び比較例1で得られた粘着剤組成物で作製した粘着シートを、130℃で2時間硬化させた後、両面の離型フィルムを剥離して粘着層を得た。この粘着層の25℃での貯蔵弾性率(E’)及び損失正接(tanδ)の測定を、固体粘弾性アナライザー(ティー・エイ・インスツルメント株式会社製、RSA-III)を用い、JIS K7244-1に準拠した動的粘弾性測定法(アタッチメントモード:圧縮モード、周波数:1Hz、温度:-50℃~150℃、昇温速度:5℃/分)にて行った。結果を図4に示した。図4の貯蔵弾性率(E’)と損失正接(tanδ)の温度依存性のグラフからも明らかなように、比較例1の粘着層よりも実施例1の粘着層の方が軟化点が高かった。この結果から、実施例1で得られた粘着剤組成物で作製した粘着層は、高温熱水環境下においても優れた接着強度を保持できることがわかる。
2A 第1離型フィルム
2B 第2離型フィルム
10 粘着シート
Claims (14)
- エポキシ樹脂とアクリル粒子と硬化剤とを少なくとも含み、前記アクリル粒子が、ブタジエン系ゴムとポリメタクリレート又はポリアクリレートとを有するコアシェル構造体であることを特徴とする粘着剤組成物。
- 前記エポキシ樹脂がビスフェノールA型エポキシ樹脂である、請求項1に記載の粘着剤組成物。
- 前記アクリル粒子が、平均粒径200nm以下である、請求項1又は2に記載の粘着剤組成物。
- 前記粘着剤組成物の総質量を100%としたときに、前記アクリル粒子の配合比率が、質量基準において3%以上、33%以下である、請求項1又は2に記載の粘着剤組成物。
- 前記アクリル粒子が反応性官能基を有する、請求項1又は2に記載の粘着剤組成物。
- 前記反応性官能基がエポキシ基である、請求項5に記載の粘着剤組成物。
- 前記アクリル粒子のブタジエン系ゴムとポリメタクリレート又はポリアクリレートが、エポキシ変性ポリメタクリレート又はエポキシ変性ポリアクリレートである、請求項1又は2に記載の粘着剤組成物。
- 第1離型フィルムと第2離型フィルムとの間に粘着層を備え、
前記粘着層が、エポキシ樹脂とアクリル粒子と硬化剤とを少なくとも含み、前記アクリル粒子が、ブタジエン系ゴムとポリメタクリレート又はポリアクリレートとを有するコアシェル構造体であることを特徴とする、粘着シート。 - 前記エポキシ樹脂がビスフェノールA型エポキシ樹脂である、請求項8に記載の粘着シート。
- 前記アクリル粒子が、平均粒径200nm以下である、請求項8又は9に記載の粘着シート。
- 前記粘着剤層の総質量を100%としたときに、前記アクリル粒子の配合比率が、質量基準において3%以上、33%以下である、請求項8又は9に記載の粘着シート。
- 前記アクリル粒子が反応性官能基を有する、請求項8又は9に記載の粘着シート。
- 前記反応性官能基がエポキシ基である、請求項12に記載の粘着シート。
- 前記アクリル粒子のブタジエン系ゴムとポリメタクリレート又はポリアクリレートが、エポキシ変性ポリメタクリレート又はエポキシ変性ポリアクリレートである、請求項8又は9に記載の粘着シート。
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