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WO2013031678A1 - Composition de résine durcissable - Google Patents

Composition de résine durcissable Download PDF

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Publication number
WO2013031678A1
WO2013031678A1 PCT/JP2012/071425 JP2012071425W WO2013031678A1 WO 2013031678 A1 WO2013031678 A1 WO 2013031678A1 JP 2012071425 W JP2012071425 W JP 2012071425W WO 2013031678 A1 WO2013031678 A1 WO 2013031678A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
curable resin
resin composition
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/071425
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English (en)
Japanese (ja)
Inventor
佑基 比舎
泰則 林
慶次 後藤
公彦 依田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Denka Co Ltd
Original Assignee
Denki Kagaku Kogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Denki Kagaku Kogyo KK filed Critical Denki Kagaku Kogyo KK
Priority to JP2013531280A priority Critical patent/JP6035241B2/ja
Priority to KR1020147002780A priority patent/KR101942546B1/ko
Priority to CN201280041431.1A priority patent/CN103764701A/zh
Publication of WO2013031678A1 publication Critical patent/WO2013031678A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas

Definitions

  • the present invention relates to a curable resin composition.
  • Examples of touch panels mounted on a display body such as an LCD include a resistance film type, a capacitance type, an electromagnetic induction type, and an optical type. On these touch panels, there are cases where a decorative board for improving the appearance design and an icon sheet for designating a touch position are pasted together.
  • the capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.
  • the UV curable resin of Patent Document 2 is a highly elastic resin based on a rigid skeleton monomer such as isobornyl (meth) acrylate, it can withstand expansion and contraction of an adherend in a high temperature reliability test. It is considered that peeling cannot occur.
  • the present inventors have a compound having one mercapto group in the molecule which is one or more selected from the group consisting of alkanethiol and carboxythiol in the compound having a mercapto group which is one component of the curable resin composition. It has been confirmed that a curable resin composition having high adhesion durability can be obtained when using (for example, see Examples described later). On the other hand, in Patent Documents 3 to 5 described above, since such a specific type of compound having a mercapto group is not used, it is considered that the flexibility and adhesiveness of the curable resin composition cannot be controlled.
  • a curable resin composition is provided.
  • the curable resin composition which contains (meth) acrylates other than said (A) and (B) as a (E) component further to the said curable resin composition is provided.
  • the curable resin composition whose said (E) component is a trimethylol propane tri (meth) acrylate and / or tricyclodecane dimethanol (meth) acrylate is provided.
  • numerator of said (C) is alkanethiol shown by following formula (1) is provided.
  • the adhesive composition which consists of the said curable resin composition is provided.
  • the hardening body of the said adhesive composition is provided.
  • covered or joined by the said hardening body is provided.
  • the adherend is at least one selected from the group consisting of triacetylcellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal.
  • the touch-panel laminated body formed by bonding a to-be-adhered body with the said adhesive composition is provided.
  • the liquid crystal panel laminated body which bonded together the to-be-adhered body with the said adhesive composition is provided.
  • the display using the said touchscreen laminated body is provided.
  • the display using the said liquid crystal panel laminated body is provided.
  • the curable resin composition of the present invention exhibits high adhesion durability.
  • the polyfunctional (meth) acrylate means (meth) acrylate in which two or more (meth) acryloyl groups are contained in one molecule.
  • the monofunctional (meth) acrylate means (meth) acrylate in which one (meth) acryloyl group is contained in one molecule.
  • a liquid oligomer having a (meth) acryloyl group is preferable.
  • this liquid oligomer an oligomer having at least two (meth) acryloyl groups in the molecule can be suitably used from the viewpoint of curability.
  • the number of (meth) acryloyl groups in one molecule is preferably 2 to 6, more preferably 2 to 4, and most preferably 2.
  • the (meth) acryloyl group may be located at both ends or one end of the oligomer of the component (A).
  • the (meth) acryloyl group refers to an acryloyl group or a methacryloyl group.
  • the oligomer having a (meth) acryloyl group is not particularly limited, and examples thereof include urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polyether (meth) acrylate oligomers, and epoxy (meth) acrylates. Examples thereof include one or more (meth) acrylate oligomers selected from the group consisting of oligomers, diene polymer (meth) acrylate oligomers, and hydrogenated products of diene polymer (meth) acrylates.
  • the main chain skeleton of the oligomer having a (meth) acryloyl group is not particularly limited.
  • a urethane type (meth) acrylate oligomer means the (meth) acrylate oligomer which has a urethane bond in a molecule
  • the urethane-based (meth) acrylate oligomer is obtained by, for example, esterifying a polyurethane oligomer obtained by reaction of polybutadienediol, polyether polyol, polyester polyol, polycarbonate diol, and the like with polyisocyanate with (meth) acrylic acid. Obtainable.
  • Polybutadiene-modified urethane (meth) acrylate obtained by (meth) acryl modification of polybutadiene is also included in the urethane (meth) acrylate oligomer.
  • Hydrogenated polybutadiene-modified urethane (meth) acrylate obtained by (meth) acryl modification of hydrogenated polybutadiene is also included in the urethane (meth) acrylate oligomer.
  • Urethane (meth) acrylate oligomers include 1,2-polybutadiene modified urethane (meth) acrylate oligomers, polyester urethane (meth) acrylate oligomers, dibutylene glycol urethane (meth) acrylate oligomers, and polycarbonate urethane (meth).
  • An acrylate oligomer, a polyether urethane type (meth) acrylate oligomer, etc. are mentioned.
  • Polyester-based (meth) acrylate oligomers can be produced by, for example, esterifying hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acids and polyhydric alcohols with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid.
  • the polyether (meth) acrylate oligomer can be obtained, for example, by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.
  • the epoxy-based (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it.
  • a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy-based (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used.
  • diene polymer (meth) acrylate oligomer examples include, for example, SBR di (meth) acrylate obtained by (meth) acryl modification of a liquid styrene-butadiene copolymer and polymethrene obtained by (meth) acryl modification of polyisoprene.
  • examples include isoprene (meth) acrylate.
  • An oligomer having a skeleton of a hydrogenated product of a diene polymer (meth) acrylate for example, by esterifying hydroxyl groups of hydrogenated polybutadiene or hydrogenated polyisoprene with hydroxyl groups at both ends with (meth) acrylic acid.
  • the liquid oligomer which has the said (meth) acryloyl group may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the liquid oligomers from the viewpoint of curability and the like, urethane (meth) acrylate oligomers are preferable, and bifunctional urethane (meth) acrylate oligomers are more preferable.
  • the bifunctional urethane (meth) acrylate oligomer means that two (meth) acryloyl groups are contained in one molecule of the urethane (meth) acrylate oligomer.
  • the bifunctional urethane-based (meth) acrylate oligomer can be obtained by esterifying a polyurethane oligomer with (meth) acrylic acid.
  • the polyurethane oligomer can be obtained by reacting a polyether polyol, polyester polyol, polycarbonate diol or the like having two hydroxy groups in the molecule with a polyisocyanate.
  • polyether polyol having two hydroxy groups examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol (polybutylene glycol), polyhexamethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neo A compound obtained by adding ethylene oxide or propylene oxide to pentyl glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, bisphenol A, or the like can be used.
  • polyester polyol having two hydroxy groups can be obtained, for example, by reacting an alcohol component and an acid component.
  • Polyester polyols having two hydroxy groups include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (polybutylene glycol), 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neo A compound in which ethylene oxide or propylene oxide is added to pentyl glycol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, bisphenol A or the like, or a compound in which ⁇ -caprolactone is added, etc.
  • dibasic acids such as adipic acid, sebacic acid, azelaic acid, and dodecanedicarboxylic acid and their anhydrides can be used as an acid component, and the alcohol component and the acid component can be reacted and used.
  • a compound obtained by simultaneously reacting the above-mentioned alcohol component, acid component, and ⁇ -caprolactone can also be used as the polyester polyol.
  • the weight average molecular weight and number average molecular weight of the urethane-based (meth) acrylate oligomer are preferably 500 to 100,000, more preferably 1,000 to 50,000 in view of handling properties. This value is not particularly limited, but may be, for example, 500, 1000, 2000, 3000, 4000, 5000, 7000, 10000, 20000, 30000, 40000, 50000, or 100000, and within the range of any of these values. There may be.
  • the average molecular weight is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method.
  • the average molecular weight was determined by preparing a calibration curve with commercially available standard polystyrene using GPC system (SC-8010 manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent under the following conditions. .
  • Flow rate 1.0 ml / min
  • Set temperature 40 ° C
  • Sample injection volume 100 ⁇ l (sample solution concentration 1 mg / ml)
  • Liquid feeding pressure 39 kg / cm 2
  • Detector RI detector
  • the urethane-based (meth) acrylate oligomer may be represented by the following general formula (1), for example.
  • R ′ in the general formula is H or CH 3
  • the following structure in which butadiene is hydrogenated may be selected.
  • R ′ is a compound of CH 3
  • R ′ is a compound of H
  • R ′ is H
  • a structure in which the above butadiene is hydrogenated The compounds selected from can be purchased, for example, from Nippon Soda Co., Ltd. (brands are TE-2000, TEA-1000, TEAI-1000 in this order).
  • (meth) acrylates having a homopolymer glass transition temperature of ⁇ 100 to 60 ° C. include lauryl (meth) acrylate (acrylate homopolymer glass transition temperature: acrylate-30 ° C., methacrylate homopolymer glass transition temperature: ⁇ 65 ° C.
  • These (meth) acrylates can be used alone or in combination of two or more.
  • the above -100 to 60 ° C is, for example, -100, -90, -80, -70, -60, -50, -40, -30, -20, -10, 0, 10, 20, 30, 40, 50 Or 60 ° C., or in the range of any of these values.
  • Glass transition refers to a change in which a substance such as glass, which is liquid at high temperatures, suddenly increases its viscosity in a certain temperature range due to a temperature drop, almost loses fluidity and becomes an amorphous solid.
  • a measuring method of a glass transition temperature Generally, the glass transition temperature computed from the thermogravimetry, the differential scanning calorimetry, the differential calorimetry, and the dynamic viscoelasticity measurement is pointed out. Among these, dynamic viscoelasticity measurement is preferable.
  • the glass transition temperature of the (meth) acrylate homopolymer is described in J. Org. Brandrup, E.M. H. Immersut, Polymer Handbook, 2nd Ed. , J .; Wiley, New York 1975, photocuring technology data book (Technonet Books), etc.
  • the compound of the general formula (2) is preferable in terms of high adhesiveness.
  • Formula (2) Z—O—R 1 [Wherein, Z represents a (meth) acryloyl group, and R 1 represents a functional group having an aromatic ring or a hydrocarbon group having 9 to 20 carbon atoms. ]
  • the compound of the general formula (2) further improves the flexibility of the cured product and further improves the adhesion to polyethylene terephthalate and the like.
  • an ester of (meth) acrylic acid having an aromatic ring such as nonylphenyl group, nonylphenoxypolyethylene glycol group, phenoxy group, phenoxyethylene glycol group, nonyl group, isononyl group, Hydrocarbon groups having 9 to 20 carbon atoms such as decyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicodecyl group, etc.
  • esters of (meth) acrylic acid examples thereof include esters of (meth) acrylic acid.
  • a linear or branched alkyl group having 9 to 20 carbon atoms is preferred, an alkyl group having 10 to 16 carbon atoms is more preferred, an alkyl group having 11 to 14 carbon atoms is most preferred, and lauryl
  • One or more selected from the group consisting of a group and an isostearyl group is preferred.
  • One or more of these (meth) acrylates can be used.
  • the number of aromatic rings is, for example, 1, 2, or 3, and preferably one.
  • Examples of the mercapto group-containing compound in the present embodiment include the following materials.
  • Alkanethiol is a thiol having an alkyl group.
  • the alkyl group may be a straight chain structure or a branched structure.
  • alkanethiols represented by the following formula (1) are preferable.
  • decanethiol and / or dodecanethiol are preferred.
  • Carboxythiol is a thiol having a carboxyl group.
  • carboxythiol represented by the following formula (2) is preferable.
  • ROOC (CH 2 ) p SH Formula (2) R is hydrogen or a hydrocarbon group having 1 to 19 carbon atoms, p is an integer
  • the R hydrocarbon group preferably has 2 to 16 carbon atoms, and more preferably 5 to 12 carbon atoms.
  • P is preferably from 1 to 30, and more preferably from 1 to 2.
  • carboxythiol examples include thioglycolic acid, ⁇ -mercaptopropionic acid, thioglycolic acid ester (methyl thioglycolate, octyl thioglycolate, etc.), ⁇ -mercaptopropionic acid ester (methyl-3-mercaptopropionate, methyl- 3-mercaptopropionate, n-octyl-3-mercaptopropionate, stearyl-3-mercaptopropionate) and the like.
  • carboxythiols thioglycolic acid and / or ⁇ -mercaptopropionic acid are preferred.
  • the photopolymerization agent is not particularly limited as long as it initiates polymerization of (meth) acrylate having a homopolymer glass transition temperature of ⁇ 100 to 60 ° C.
  • Examples of the photopolymerization initiator include an ultraviolet polymerization initiator and a visible light polymerization initiator, both of which are used without limitation.
  • Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone.
  • Examples of visible light polymerization initiators include acylphosphine oxide, thioxanthone, metallocene, quinone, and ⁇ -aminoalkylphenone.
  • Photopolymerization initiators include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl Rupropan-1-one, camphorquinone, 2,4,6-tri
  • the curable resin composition of the present embodiment has (A) a urethane-based (meth) acrylate oligomer, a polyester-based (meth) as the component (E) for the purpose of further improving the adhesion to each adherend.
  • (E) component ((meth) acrylates other than (A) and (B)) monofunctional (meth) acrylate, polyfunctional such as bifunctional, trifunctional, tetrafunctional, pentafunctional, and hexafunctional ( It can be used in various ways such as (meth) acrylate. Among these, monofunctional (meth) acrylate or bifunctional (meth) acrylate is preferable.
  • (E) component of this embodiment as monofunctional (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) ) Acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonyl Enoxyethyl (meth) acryl
  • dicyclopentenyloxyethyl (meth) acrylate dicyclosilane is used for the purpose of improving adhesiveness to polyolefins including cycloolefin polymers.
  • examples thereof include (meth) acrylates having a dicyclopentenyl group such as cyclopentenyloxypropyl (meth) acrylate and dicyclopentenyl (meth) acrylate.
  • (meth) acrylates and / or isobornyl (meth) acrylates having a dicyclopentenyl group are more preferable in terms of improving the adhesion to cycloolefin.
  • the polyfunctional (meth) acrylate di (meth) acrylated isocyanurate, tri (meth) acrylated isocyanurate, 1,3-dibutylene glycol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, EO (ethylene oxide) modified bisphenol A di (meth) acrylate , Diethylene glycol di (meth) acrylate, ECH (epichlorohydrin) modified hexahydrophthalic acid di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol di (meth) acrylate, caprolactone modified hydroxypivalin Acid Este Luneopentyl glycol di (
  • examples of the polyfunctional (meth) acrylate include (meth) acrylate having a dicyclopentenyl group such as dicyclopentenyl di (meth) acrylate.
  • examples of the polyfunctional (meth) acrylates in the component (E) trimethylolpropane tri (meth) acrylate and / or tricyclodecane dimethanol (meth) acrylate is more preferable in terms of oligomer solubility.
  • a silane coupling agent can be contained for the purpose of improving the adhesion to glass.
  • the curable resin composition of this embodiment includes (A) a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, a polyether (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, and a diene polymer system.
  • the curable resin composition of the present embodiment can be cured by ultraviolet rays or visible light.
  • the mass ratio of the component (A) and the component (B) is such that the adhesiveness is increased and the curability is improved.
  • the numerical value of the component (A) when expressing this ratio is not particularly limited, and may be, for example, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95, It may be within the range of these values.
  • the numerical value of the component (B) when expressing this ratio is not particularly limited, and may be, for example, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95, and It may be within the range of any value.
  • Component (C) is preferably used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of component (A), component (B) and component (E) used as necessary. 1 to 8 parts by mass is more preferable.
  • the amount used is not particularly limited, and may be, for example, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 15, either It may be within the range of the value of.
  • Component (D) is preferably used in an amount of 0.1 to 20 parts by weight per 100 parts by weight of component (A), component (B), and component (E) used as necessary. 2 to 10 parts by mass is more preferable.
  • the amount used is not particularly limited, but may be, for example, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25. May be within the range of any of these values.
  • the amount of component (E) used is preferably 1 to 30 parts by weight, more preferably 5 to 15 parts by weight, based on a total of 100 parts by weight of component (A) and component (B).
  • the amount used is not particularly limited, and may be, for example, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, or 35. It may be within the range of values.
  • the curable resin composition of this embodiment can use various paraffins in order to quickly cure the portion in contact with air.
  • a commercially available antioxidant containing a polymerization inhibitor can be used.
  • the curable resin composition in this embodiment can be used as an adhesive composition.
  • a to-be-adhered body can be joined or coat
  • the cured product is obtained, for example, by irradiating the adhesive composition with UV.
  • a to-be-adhered body about various materials of a to-be-adhered body, 1 or more types chosen from the group which consists of polyolefin, glass, a metal, such as a triacetyl cellulose, a fluorine-type polymer, polyester, a polycarbonate, a cycloolefin polymer, is preferable, and consists of a polycarbonate, polyolefin, glass.
  • a metal such as a triacetyl cellulose, a fluorine-type polymer, polyester, a polycarbonate, a cycloolefin polymer, is preferable, and consists of a polycarbonate, polyolefin, glass.
  • a metal such as a triacetyl cellulose, a fluorine-type polymer, polyester, a polycarbonate, a cycloolefin polymer, is preferable, and consists of a polycarbonate, polyolefin, glass.
  • the cured body bonded with the curable resin composition of the present embodiment can be reworked (reused) after being completely cured.
  • the rework method is not particularly limited, but the adherends are disassembled by applying a load of 0.01 to 100 N between the one or two kinds of adherends bonded together, and the adherend after disassembly The body can be reused.
  • a (meth) acrylate oligomer (A) that is at least one selected from the group consisting of oligomers having a skeleton of an acrylate hydrogenated product, (A-1) 1,2-polybutadiene-modified urethane methacrylate oligomer (“TE-2000” manufactured by Nippon Soda Co., Ltd.) (Number average molecular weight 2000 in terms of polystyrene by GPC, bifunctional methacrylate oligomer).
  • A-2) Mixture of acrylic ester polymer and urethane acrylate oligomer (“PM-654” manufactured by Osaka Organic Chemical Industry Co., Ltd.) (Number average molecular weight of 20000 in terms of polystyrene by GPC, bifunctional acrylate oligomer) (A-3) Polyester urethane acrylate oligomer (“KHP-17” manufactured by Negami Kogyo Co., Ltd.) (weight average molecular weight 40000 in terms of polystyrene by GPC, bifunctional acrylate oligomer) (A-4) Dibutylene glycol urethane-based acrylate oligomer (“UV-3000B” manufactured by Nippon Synthetic Chemical Co., Ltd.
  • PET Polyethylene terephthalate
  • PET adhesion evaluation (peeling adhesive strength between polyethylene terephthalate test pieces)
  • Biaxially stretched PET film (Lumirror T60, average thickness 190 ⁇ m, manufactured by Toray Industries, Inc.) test pieces (50 mm ⁇ 10 mm ⁇ 0. 19 mm) were bonded using a curable resin composition as an adhesive composition, with an adhesive layer thickness of 30 ⁇ m and an adhesive area of 40 mm long ⁇ 10 mm wide. After curing by light irradiation, by pulling the two non-adhered film end portions of the test piece bonded with an adhesive, the film-adhered portions are peeled off, and the initial 180 ° peel adhesion strength was measured.
  • the light irradiation conditions followed the method described in [Photocurability].
  • the peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • the tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • the bond strength was measured.
  • the light irradiation conditions followed the method described in [Photocurability].
  • the peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • Triacetylcellulose (TAC) film (average thickness 40 ⁇ m, manufactured by Fuji Film) test piece (width 50 mm ⁇ length 10 mm ⁇ A thickness of 0.04 mm was bonded to each other with the adhesive layer having a thickness of 10 ⁇ m and a bonding area of 40 mm in length and 10 mm in width by using the curable resin composition as an adhesive composition. After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed.
  • the bond strength was measured.
  • the light irradiation conditions followed the method described in [Photocurability].
  • the peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.
  • PVDF film (average thickness 40 ⁇ m, “DX film” manufactured by Denki Kagaku Kogyo Co., Ltd.) test piece (width 50 mm ⁇ length 10 mm ⁇ thickness) 0.04 mm) were bonded to each other using a curable resin composition as an adhesive composition with an adhesive layer thickness of 10 ⁇ m and an adhesive area of 40 mm long ⁇ 10 mm wide. After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed.
  • the bond strength was measured.
  • the light irradiation conditions followed the method described in [Photocurability].
  • the peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.
  • the tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • an adhesive composition “G-55” manufactured by Denki Kagaku Kogyo Co., Ltd. was used on the Tempax test piece side, and a galvanized steel sheet (width 100 mm ⁇ length 25 mm ⁇ A thickness of 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) was adhered.
  • the galvanized steel sheet was chucked, and the initial tensile shear bond strength was measured.
  • the tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • Tempax glasses 25 mm x 25 mm x 2 mm were used as curable resin compositions as adhesive compositions, The adhesive layer was bonded and cured with a thickness of 100 ⁇ m and an adhesive area of 1.0 mm 2 . The light irradiation conditions followed the method described in [Photocurability]. After curing, the test piece bonded with the adhesive composition was exposed to an environment of 85 ° C. and 85% relative humidity for 1000 hours using a constant temperature and humidity chamber. The tensile shear bond strength was measured using the test piece after exposure. The appearance of the bonded part was visually observed to determine whether it was yellowed.
  • an adhesive composition “G-55” manufactured by Denki Kagaku Kogyo Co., Ltd. was used on the Tempax test piece side, and a galvanized steel sheet (width 100 mm ⁇ length 25 mm ⁇ thickness 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) ) was adhered.
  • the galvanized steel sheet was chucked, and the initial tensile shear bond strength was measured.
  • the tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • the present invention has high adhesiveness. Since the present invention has such flexibility that it can follow the deformation of the adherend in a heated atmosphere, it has a high resistance to moist heat. When DMDO which is a compound having two or more mercapto groups is used, flexibility and adhesiveness are small.
  • the present invention since bubbles are hardly mixed, sufficient adhesion can be imparted, and a transparent substrate can be bonded or a printed portion can be bonded. Since the present invention has a high resistance to moist heat, it can be used in a heated atmosphere. The present invention has great industrial applicability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une composition de résine durcissable montrant une durabilité de l'adhérence élevée. La composition de résine durcissable contient : un oligomère de type (méth)acrylate (A) sélectionné dans le groupe constitué par les oligomères de (méth)acrylate à base d'uréthane, les oligomères de (méth)acrylate à base de polyester, les oligomères de (méth)acrylate à base de polyéther, les oligomères de (méth)acrylate à base d'époxy, les oligomères de (méth)acrylate à base de diènes et les oligomères présentant une chaîne principale du produit hydrogéné d'un (méth)acrylate à base d'un polymère de diènes ; un (méth)acrylate (B) montrant une température de transition vitreuse d'homopolymère de -100°C à 60°C ; un ou plusieurs composés (C) présentant un groupe mercapto par molécule, le(s) composé(s) étant sélectionné(s) dans le groupe constitué par les alcanethiols et les carboxythiols ; et un initiateur de photopolymérisation (D).
PCT/JP2012/071425 2011-08-26 2012-08-24 Composition de résine durcissable Ceased WO2013031678A1 (fr)

Priority Applications (3)

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JP2013531280A JP6035241B2 (ja) 2011-08-26 2012-08-24 硬化性樹脂組成物
KR1020147002780A KR101942546B1 (ko) 2011-08-26 2012-08-24 경화성 수지 조성물
CN201280041431.1A CN103764701A (zh) 2011-08-26 2012-08-24 固化性树脂组合物

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WO2016190361A1 (fr) * 2015-05-26 2016-12-01 デンカ株式会社 Composition
WO2018159110A1 (fr) * 2017-02-28 2018-09-07 デクセリアルズ株式会社 Procédé de fabrication de corps stratifié et composition de résine photodurcissable
JP2019151774A (ja) * 2018-03-06 2019-09-12 東亞合成株式会社 活性エネルギー線硬化型粘着剤組成物
WO2022230874A1 (fr) * 2021-04-26 2022-11-03 デンカ株式会社 Composition
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JP2013203843A (ja) * 2012-03-28 2013-10-07 Kyoritsu Kagaku Sangyo Kk 加飾印刷された前面板と光学表示パネル又はタッチパネルとの貼り合せ用光硬化型樹脂組成物及びこれを用いて貼り合わせた光学表示体又はタッチセンサー
JP2014189575A (ja) * 2013-03-26 2014-10-06 Hitachi Chemical Co Ltd 液状硬化性樹脂組成物、画像表示用装置、及び画像表示用装置の製造方法
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WO2016190361A1 (fr) * 2015-05-26 2016-12-01 デンカ株式会社 Composition
CN105018016A (zh) * 2015-09-03 2015-11-04 侯颖 一种皮革用高强度胶黏剂组合物制备方法
JP2018140601A (ja) * 2017-02-28 2018-09-13 デクセリアルズ株式会社 積層体の製造方法、及び光硬化性樹脂組成物
CN110234506A (zh) * 2017-02-28 2019-09-13 迪睿合株式会社 层合体的制备方法及光固化性树脂组合物
WO2018159110A1 (fr) * 2017-02-28 2018-09-07 デクセリアルズ株式会社 Procédé de fabrication de corps stratifié et composition de résine photodurcissable
CN110234506B (zh) * 2017-02-28 2021-05-11 迪睿合株式会社 层合体的制备方法及光固化性树脂组合物
JP2019151774A (ja) * 2018-03-06 2019-09-12 東亞合成株式会社 活性エネルギー線硬化型粘着剤組成物
JP7077673B2 (ja) 2018-03-06 2022-05-31 東亞合成株式会社 活性エネルギー線硬化型粘着剤組成物
WO2022230874A1 (fr) * 2021-04-26 2022-11-03 デンカ株式会社 Composition
JPWO2022230874A1 (fr) * 2021-04-26 2022-11-03
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WO2025205577A1 (fr) * 2024-03-29 2025-10-02 積水フーラー株式会社 Composition de résine photopodurcissable

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CN103764701A (zh) 2014-04-30
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JP6035241B2 (ja) 2016-11-30
JPWO2013031678A1 (ja) 2015-03-23

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