WO2018051868A1 - Ultraviolet-curable resin composition and laminated body - Google Patents

Ultraviolet-curable resin composition and laminated body Download PDF

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Publication number
WO2018051868A1
WO2018051868A1 PCT/JP2017/032194 JP2017032194W WO2018051868A1 WO 2018051868 A1 WO2018051868 A1 WO 2018051868A1 JP 2017032194 W JP2017032194 W JP 2017032194W WO 2018051868 A1 WO2018051868 A1 WO 2018051868A1
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Prior art keywords
epoxy compound
plate
polyfunctional
mass
parts
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PCT/JP2017/032194
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French (fr)
Japanese (ja)
Inventor
行壮 松野
真介 吉田
容三 松川
守雄 中谷
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パナソニックＩｐマネジメント株式会社
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Publication of WO2018051868A1 publication Critical patent/WO2018051868A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08G59/20—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 epoxy compounds used
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/36—Epoxy compounds containing three or more epoxy groups together with mono-epoxy compounds
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes

Definitions

  • the present invention relates to an ultraviolet curable resin composition and a laminate.
  • this invention relates to the laminated body utilized as a display apparatus etc., and the ultraviolet curable resin composition used for this.
  • a laminate including a transparent plate and a display plate has been proposed as a display device for portable electronic terminals such as smartphones and mobile phones.
  • the transparent plate has a function of covering and protecting the display plate, and a plastic plate or a glass plate is used.
  • the display board has a function of displaying characters and images, and a liquid crystal panel or an organic EL panel is used.
  • the transparent plate and the display plate are bonded and fixed with a transparent adhesive.
  • OCA Optical Clear Adhesive
  • OCR Optical Clear Resin
  • LCD Liquid Crystal Display
  • OLED Organic Light Emitting Diode
  • FIG. 3A to 3C show a manufacturing process of a laminate using OCA.
  • the OCA 11 of the film is pressed and adhered to one side of the transparent plate 10 with a roller 12.
  • FIG. 3B the surface of the OCA 11 laminated on the transparent plate 10 is pressed and adhered to one side of the display plate 13 with a roller 14.
  • the laminate 100 in which the transparent plate 10 and the display plate 13 are bonded and fixed by the OCA 11 can be obtained (FIG. 3C).
  • FIG. 4A to 4E show a manufacturing process of a laminated body using OCR.
  • liquid OCR 21 is applied to one side of the transparent plate 20.
  • FIG. 4B the transparent plate 20 and the display plate 23 are aligned (positioned) with one side of the transparent plate 20 coated with the OCR 21 facing the one side of the display plate 23.
  • FIG. 4C the transparent plate 20 and the display plate 23 are overlapped.
  • the UV emitted from the UV irradiation device 25 is applied to the transparent plate 20, and the UV that has passed through the transparent plate 20 is applied to the OCR 21 between the transparent plate 20 and the display plate 23.
  • the OCR 21 is cured, and the transparent plate 20 and the display plate 23 are bonded by the cured OCR 21. In this way, it is possible to obtain a laminate 200 in which the transparent plate 20 and the display plate 23 are bonded and fixed by the cured OCR 21 (FIG. 4E).
  • Patent Document 1 a bonding process using precure OCR has been proposed (see Patent Document 1).
  • the content described in Patent Document 1 is that after applying a liquid OCR on one side of a transparent plate, before superimposing the transparent plate and the display plate, UV irradiation is applied to the OCR to make it semi-cured, and then the transparent plate This is a technique of bonding the display boards.
  • the OCR is cured at a portion where UV can be transmitted and irradiated.
  • the part that cannot be irradiated without UV transmission is not cured, the adhesion strength between the transparent plate and the display panel is reduced, or in some cases, the uncured OCR sticks out of the laminate and the periphery of the laminate There was a problem of polluting.
  • the adhesion strength may be reduced as compared with a general OCR.
  • the present invention has been made in view of the above points, and has a high adhesion strength between layers of a laminate, an ultraviolet curable resin composition excellent in rework and antifouling properties at the time of producing the laminate, and a laminate using the same.
  • the purpose is to provide a body.
  • the ultraviolet curable resin composition according to the present invention is: A polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound;
  • the total content of the polyfunctional epoxy compound and the polyfunctional oxetane compound is 100 parts by mass or more with respect to 100 parts by mass of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound.
  • the amount of the monofunctional epoxy compound is 70 parts by mass or less and 5 parts by mass or more.
  • the monofunctional epoxy compound contains a monofunctional epoxy compound having a hydrocarbon skeleton having 7 to 20 carbon atoms, At least one of the polyfunctional epoxy compound and the monofunctional epoxy compound contains an aromatic benzene ring-containing epoxy compound, Content of the said aromatic benzene ring containing epoxy compound is 1 to 40 mass parts with respect to 100 mass parts of total amounts of the said polyfunctional epoxy compound, the said monofunctional epoxy compound, and the said polyfunctional oxetane compound. .
  • the laminate according to the present invention is A first plate that does not transmit ultraviolet light; A second plate that does not transmit ultraviolet light; A laminated body provided between the first plate and the second plate and having a fixing layer for fixing the first plate and the second plate;
  • the fixed layer is a cured product of an ultraviolet curable resin composition that is provided between the first plate and the second plate and bonds the first plate and the second plate so that they can be reworked,
  • the ultraviolet curable resin composition includes a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound, and a total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound.
  • the total content of the polyfunctional epoxy compound and the polyfunctional oxetane compound is 30 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass, and the monofunctional epoxy compound contains 70 parts by mass or less and 5 parts by mass or more.
  • the monofunctional epoxy compound contains a monofunctional epoxy compound having a hydrocarbon skeleton having 7 to 20 carbon atoms, At least one of the polyfunctional epoxy compound and the monofunctional epoxy compound contains an aromatic benzene ring-containing epoxy compound, The content of the aromatic benzene ring-containing epoxy compound is 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. is there.
  • FIG. 1A is a schematic exploded perspective view showing an embodiment according to the present invention.
  • FIG. 1B is a schematic sectional view showing an embodiment according to the present invention.
  • FIG. 2A is a schematic perspective view showing an adhesive placement step in the manufacturing method of one embodiment according to the present invention.
  • FIG. 2B is a schematic perspective view showing an irradiation step in the manufacturing method of one embodiment according to the present invention.
  • FIG. 2C is a schematic perspective view showing an alignment process in the manufacturing method according to the embodiment of the present invention.
  • FIG. 2D is a schematic perspective view showing a bonding step in the manufacturing method according to the embodiment of the present invention.
  • FIG. 2E is a schematic perspective view showing a curing process in the manufacturing method according to the embodiment of the present invention.
  • 3A to 3C are schematic perspective views showing a manufacturing process of a conventional laminate.
  • 4A to 4E are schematic perspective views showing a manufacturing process of a conventional laminate.
  • (Laminate) 1A and 1B show a laminate 300.
  • FIG. The laminated body 300 is formed by layering the first plate 30, the second plate 31, and the fixed layer 32.
  • the laminated body 300 is formed as a display device for portable electronic terminals such as smartphones and mobile phones, for example.
  • the first plate 30 is formed as a transparent plate 301 and the second plate 31 is used as a display plate 311. Is formed.
  • the fixed layer 32 is formed of a cured product of an ultraviolet curable resin composition.
  • symbol 33 is a decoration printing layer.
  • the transparent plate 301 has a function of covering and protecting the display plate 311, and a plastic plate or glass plate made of polycarbonate or acrylic resin is used.
  • the display plate 311 has a function of displaying characters and images, and a liquid crystal panel display, an organic EL panel display, or the like is used.
  • a display plate 311 including a backlight 312, a liquid crystal panel 313, and a color filter 314 can be exemplified.
  • the fixed layer 32 is provided between the first plate 30 and the second plate 31 and adheres and fixes the first plate 30 and the second plate 31.
  • the first plate 30 and the second plate 31 are formed by the fixed layer 32 so as not to be displaced from each other, and are formed so as not to be easily separated from each other.
  • the first plate 30 and the second plate 31 are arranged so as to be parallel to each other.
  • the first plate 30 and the second plate 31 do not have to be strictly parallel, and may be within a range that can be regarded as being substantially parallel.
  • the first plate 30 and the second plate 31 do not transmit ultraviolet rays.
  • “does not transmit ultraviolet rays” means that the transmittance of ultraviolet rays is 0% or more and 5% or less.
  • the transparent plate 301 preferably has a total light transmittance of 85% or more and 100% or less, so that characters and images displayed on the display plate 311 are easily visible through the transparent plate 301.
  • the fixed layer 32 preferably has a total light transmittance of 85% or more and 100% or less, so that characters and images displayed on the display plate 311 can be easily seen through the transparent plate 301 and the fixed layer 32. .
  • the fixing layer 32 preferably has a thickness of 10 ⁇ m or more and 10 mm or less. This makes it difficult for the fixing layer 32 to break, and allows the first plate 30 and the second plate 31 to be firmly fixed.
  • the fixed layer 32 preferably has a storage elastic modulus at a temperature of 20 ° C. of 0.001 MPa or more and 0.1 MPa or less. This makes it easy to firmly fix the first plate 30 and the second plate 31 to each other. It becomes easy to prevent the separation and displacement of the plate 30 and the second plate 31.
  • the fixing layer 32 preferably has an adhesion strength (adhesive strength) with the second plate 31 of 10 N / cm 2 or more and 150 N / cm 2 or less, thereby strengthening the first plate 30 and the second plate 31. It becomes easy to fix, and it becomes easy to prevent peeling and misalignment of the first plate 30 and the second plate 31.
  • the ultraviolet curable resin composition cures when irradiated with ultraviolet rays, and forms the fixed layer 32 by curing.
  • the ultraviolet curable resin composition contains at least a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound.
  • the polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule, and may be solid or liquid.
  • polybutadiene epoxy resin aliphatic epoxy compound, epoxy-modified silicone compound, alicyclic epoxy compound, alcohol type epoxy compound such as hydrogenated bisphenol A type epoxy compound, epoxidized polybutadiene compound, bisphenol A type epoxy Resin, bisphenol type epoxy compound such as bisphenol F type epoxy resin, naphthalene type epoxy compound, biphenyl type epoxy compound, phenol novolac type epoxy compound, cresol novolak type epoxy compound and other novolak type epoxy compound, epoxidized styrene-butadiene-styrene block Copolymer, glycidylamine type epoxy compound, heterocyclic epoxy compound, multifunctional epoxy compound, glycidyl ether type epoxy compound, group Glycidyl ester type epoxy compounds, halogenated epoxy compounds such as brominated epoxy compound,
  • bisphenol A type epoxy compound bisphenol A type epoxy compound, naphthalene type epoxy compound, alicyclic epoxy compound, and the like can be mentioned because photocationic polymerization is higher and photocuring proceeds more efficiently even with a small amount of light.
  • These polyfunctional epoxy compounds may be used independently and 2 or more types may be used together.
  • a bifunctional epoxy resin among the polyfunctional epoxy compounds mentioned above from the viewpoint that the curing shrinkage stress is small and the adhesion of the cured product to the adherend is high.
  • a polybutadiene epoxy resin or the like from the viewpoint of being effective in reliability tests such as a thermal cycle test because of its low moisture permeability, hygroscopicity, and temperature dependency and low thermal stress.
  • the monofunctional epoxy compound has one epoxy group in one molecule and may be solid or liquid.
  • the monofunctional epoxy compound contains a monofunctional epoxy compound having a long chain hydrocarbon skeleton having at least 7 to 20 carbon atoms (hereinafter also simply referred to as a long chain monofunctional epoxy compound).
  • the monofunctional epoxy compound may contain only a long-chain monofunctional epoxy compound.
  • the monofunctional epoxy compound having a long-chain hydrocarbon skeleton is not particularly limited as long as it is a compound having a hydrocarbon skeleton having 7 to 20 carbon atoms and having one epoxy group in the chain or at the chain end.
  • Examples include 1,2-epoxydodecane, 1,2-epoxyeicosane, 1,2-epoxydecane, 2-ethylhexyl glycidyl ether, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, glycidyl lauryl ether, and the like. It is done.
  • YED111AN”, “YED111N”, “YED188” from Mitsubishi Chemical Corporation, “Lika Resin L-200” from Shin Nippon Chemical Co., Ltd., “EX-121”, “EX-192” from Nagase ChemteX Corporation Etc. can be used.
  • a monofunctional epoxy compound having a hydrocarbon skeleton having 11 to 15 carbon atoms from the viewpoint of easy adjustment of viscosity and delayed curing.
  • the ultraviolet curable resin composition contains an aromatic benzene ring-containing epoxy compound.
  • the aromatic benzene ring-containing epoxy compound has the function of improving the adhesive strength of the ultraviolet curable resin composition, but decomposes and develops color when exposed to a long period of time at high temperatures. It is thought that the colorability of the can be adjusted.
  • the aromatic benzene ring-containing epoxy compound is not particularly limited as long as it has one or more epoxy groups (rings) in one molecule, and may be solid or liquid. .
  • the aromatic benzene ring-containing epoxy compound can be used without particular limitation as long as it has one or more aromatic benzene rings in one molecule.
  • the ultraviolet curable resin composition can contain an aromatic benzene ring-containing epoxy compound as part or all of the polyfunctional epoxy compound.
  • the polyfunctional epoxy compound containing an aromatic benzene ring bisphenol type epoxy compound such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, naphthalene type epoxy compound, biphenyl type epoxy compound, phenol novolac type epoxy compound , Novolac epoxy compounds such as cresol novolac epoxy compounds, epoxidized styrene-butadiene-styrene block copolymers, glycidylamine epoxy compounds, heterocyclic epoxy compounds, polyfunctional epoxy compounds, glycidyl ether epoxy compounds, Halogenated epoxy compounds such as glycidyl ester type epoxy compounds and brominated epoxy compounds, rubber modified epoxy compounds, urethane modified epoxy compounds, epoxy group-containing polyesters Le compounds, epoxy group-containing polyurethane compound, an epoxy group-containing acrylic compounds.
  • the ultraviolet curable resin composition can contain an aromatic benzene ring-containing epoxy compound as a part of the monofunctional epoxy compound.
  • an aromatic benzene ring-containing epoxy compound as a part of the monofunctional epoxy compound.
  • phenyl glycidyl ether, benzyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, glycidyl 2-methoxyphenyl ether and the like can be mentioned.
  • a monofunctional epoxy compound it is possible to contain what does not correspond to any of the monofunctional epoxy compound which has the said long-chain hydrocarbon skeleton, and the said aromatic benzene ring containing epoxy compound.
  • monofunctional epoxy compounds include butyl glycidyl ether, tert-butyl glycidyl ether, 3-glycidyloxypropyl (dimethoxy) methylsilane, and allyl glycidyl ether.
  • the above aromatic benzene ring-containing epoxy compounds may be used alone or in combination of two or more.
  • the ultraviolet curable resin composition contains a polyfunctional oxetane compound.
  • the polyfunctional oxetane compound has a function of accelerating the curing reaction of the ultraviolet curable resin composition. Therefore, when it is desired to ensure appropriate curing reactivity while having delayed curing properties, It is considered that the curability can be adjusted. That is, the polyfunctional oxetane compound is a curing accelerator that improves the steepness of curing of the ultraviolet curable resin composition. Curing steepness refers to the property that the curing rate (increased viscosity per unit time) of the ultraviolet curable resin composition rapidly increases in a short time, and the time until completion of curing is increased.
  • the polyfunctional oxetane compound can be used without particular limitation as long as it has two or more oxetane groups (rings) in one molecule.
  • Such polyfunctional oxetane compounds include 3-ethyl-3-hydroxymethyl oxetane, 2-ethylhexyl oxetane, xylylene bisoxetane, 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇
  • oxetane Such as oxetane.
  • One oxetane compound can be used alone from the above, or two or more oxetane compounds can be used in combination.
  • polyfunctional oxetane compound a commercially available product can be used, and examples thereof include Oxetane series “OXT121” and “OXT221” manufactured by Toa Gosei Co., Ltd.
  • oxetane-modified silicone can also be used. Among these, it is preferable to use a material that is easy to balance the ease of viscosity adjustment and the difficulty of volatilization.
  • the ultraviolet curable resin composition according to this embodiment may contain a photopolymerization initiator.
  • the photopolymerization initiator that can be used in the present embodiment is particularly an initiator for ring-opening self-polymerization of an epoxy group (and, in some cases, an oxetane group) of an ultraviolet curable resin composition by light irradiation.
  • the photopolymerization initiator may be, for example, an ionic photoacid generator or a nonionic photoacid generator.
  • ionic photoacid generating type examples include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, and organic metals such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Complexes are mentioned. These can also use a commercially available thing.
  • organic metals such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Complexes are mentioned. These can also use a commercially available thing.
  • As an ionic photoacid generation type photocationic polymerization initiator for example, “Adekaoptomer SP150”, “Adekaoptomer SP170” and the like made by Asahi Denka Kogyo Co., Ltd.
  • Examples include the product name “CPI-210S”, the product name “UVE-1014” manufactured by General Electronics Co., and the product name “CD-1012” manufactured by Sartomer. These ionic photoacid-generating photocationic polymerization initiators may be used alone or in combination of two or more.
  • nonionic photoacid generation type is not particularly limited as the nonionic photoacid generation type photocationic polymerization initiator.
  • examples of the nonionic photoacid generating type include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimidophosphonate and the like. These nonionic photoacid-generating photocationic polymerization initiators may be used alone or in combination of two or more.
  • the ultraviolet curable resin composition further contains an elastomer as necessary.
  • the elastomer changes the physical properties and chemical properties of the cured product (fixed layer 32) of the ultraviolet curable resin composition. That is, the cured product of the ultraviolet curable resin composition containing an elastomer has an improved strength, a reduced elastic modulus, and an improved elongation rate compared to a cured product of an ultraviolet curable resin composition that does not contain an elastomer. Changes in physical properties occur.
  • the cured product of the ultraviolet curable resin composition containing the elastomer has a polar group in the elastomer that adheres to the adherend (for example, the first material, for example, as compared with the cured product of the ultraviolet curable resin composition that does not contain the elastomer.
  • Changes in chemical properties such as strengthening the chemical interaction between the plate 30 and the second plate 31) or forming a chemical bond with the adherend by the cationically polymerizable substituent in the elastomer occur.
  • the adhesion adhesion (adhesive strength) between the cured product of the ultraviolet curable resin composition and the adherend may be improved.
  • the elastomer is formed of various polymer materials such as polyolefin, polystyrene, polyester, polyurethane, and silicone.
  • these elastomers may be modified with a substituent having a large polarity such as a carboxyl group, a hydroxyl group, a cyano group, a thiol group, or an amino group, or may be modified with a cationic polymerizable substituent such as an epoxy group or an oxetane group. Then, it is more preferable. This is because the modified elastomer may have improved physical and chemical properties as compared to the case where it has not been modified.
  • One type of elastomer can be used alone, or two or more types can be used in combination.
  • the form of the elastomer in the ultraviolet curable resin composition is not particularly limited, and may be a particle, a dissolved state, or a combination of both particles and a dissolved state. Good. Further, by selecting a colorless elastomer, it is possible to reduce the optical influence of the elastomer added to the ultraviolet curable resin composition. Moreover, the optical influence by the elastomer added in the ultraviolet curable resin composition can be reduced by selecting what has a translucency comparable as the hardened
  • Colorless means that the value of the color difference ⁇ E * between the elastomer and the ultraviolet resin composition to which the elastomer is added is 3.2 or less, further 1.6 or less, and further 0.8 or less. If the value of the color difference ⁇ E * is 3.2 or less, and further 1.6 or less, it is an allowable color difference from the viewpoint of reproducibility of general visual inspection and the like, and it is considered that there is substantially no coloring due to the elastomer.
  • JIS L 0840 and JIS L 0805 may be referred to for the color difference measurement method and evaluation method. Further, the transparency of the cured product can be increased by reducing the light scattering property of the elastomer.
  • the elastomer in the cured product of the ultraviolet curable resin composition containing the elastomer, the elastomer has little effect on the transparency if the haze value is 10% or less, further 8% or less, and 5% or less. That is, the elastomer may be substantially transparent (that is, less turbid).
  • the ultraviolet curable resin composition may further contain various commonly used additives as necessary.
  • additives include, for example, silane coupling agents; inorganic fillers such as aluminum oxide, silicon oxide, calcium carbonate, and magnesium oxide; polymerization accelerators such as peroxides and azo compounds; Cationic, anionic, nonionic and amphoteric surfactants; thixotropic agents; coupling agents; flame retardants such as antimony and bromo compounds; colorants such as inorganic pigments, organic pigments and dyes Is mentioned.
  • the method for producing the ultraviolet curable resin composition is not particularly limited.
  • the blending components as described above using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, and a three roll.
  • the method of mixing is mentioned.
  • the ultraviolet curable resin composition should just mix the essential component mentioned above and the arbitrary component added as needed uniformly at the time of use, and the whole quantity is mixed at the time of distribution, storage, etc. There is no need to be. That is, depending on the situation such as distribution and storage, it may be divided into two or more types and blended immediately before use.
  • the ultraviolet curable resin composition is preferably in a liquid state immediately after mixing all necessary components.
  • the ultraviolet curable resin composition has a total of 30 parts by mass or more of the polyfunctional epoxy compound and the polyfunctional oxetane compound with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. It is contained in an amount of up to 70 parts by mass and contains up to 5 parts by mass of a monofunctional epoxy compound.
  • the ultraviolet curable resin composition is 1 part by mass or more and 30 parts by mass or less of the polyfunctional oxetane compound with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. More preferably, it is blended so as to be 3 parts by mass or more and 10 parts by mass or less.
  • blending a polyfunctional oxetane compound in 1 mass part or more and 30 mass parts or less it becomes possible to adjust moderately the cure reaction rate of an ultraviolet curable resin composition.
  • the ultraviolet curable resin composition is a polyfunctional epoxy compound with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. 0 parts by mass or more and 94 parts by mass or less, preferably 20 parts by mass or more and 92 parts by mass or less.
  • the monofunctional epoxy compound may be a monofunctional epoxy compound having a long-chain hydrocarbon skeleton
  • the ultraviolet curable resin composition is composed of a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane.
  • the monofunctional epoxy compound having a long-chain hydrocarbon skeleton is contained in an amount of 70 parts by mass or less and 5 parts by mass or more with respect to 100 parts by mass in total with the compound.
  • the ultraviolet curable resin composition has 65 masses of the monofunctional epoxy compound having a long-chain hydrocarbon skeleton with respect to 100 mass parts of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. 10 parts by mass or less. If the amount of the long-chain monofunctional epoxy compound is in the range of 70 parts by mass or less and 5 parts by mass or more, sufficient delayed hardness is obtained, and the UV curable resin composition is easily cured after a certain period of time. Become.
  • the ultraviolet curable resin composition has an aromatic benzene ring-containing epoxy compound in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound.
  • the content of the aromatic benzene ring-containing epoxy compound is the ratio between the aromatic benzene ring-containing epoxy compound formulated as a polyfunctional epoxy compound and the aromatic benzene ring-containing epoxy compound formulated as a monofunctional epoxy compound. Total amount.
  • the content of the photopolymerization initiator in the ultraviolet curable resin composition is not particularly limited, but is usually 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. It is 0.1 mass part or more and 10 mass parts or less. When the content of the photopolymerization initiator is 0.1 parts by mass or more, the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound are sufficiently polymerized, and the delay time does not become extremely long. .
  • the curing reaction of the UV curable resin composition will not be too fast, and workability (such as delayed curing) will be lost, or the deep curability will deteriorate. It does not occur (becomes a non-uniform cured product).
  • an ultraviolet curable resin composition contains an elastomer
  • the content is not particularly limited, but is 0 with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. It is preferably in the range of 1 to 100 parts by mass.
  • the content of the elastomer is within this range, it becomes easy to change the physical properties and chemical properties of the cured product (fixed layer 32) of the ultraviolet curable resin composition. That is, when the content of the elastomer deviates from the above range, it is difficult to change the physical characteristics and chemical characteristics of the cured product of the ultraviolet curable resin composition.
  • Such an ultraviolet curable resin composition is cured while being irradiated with ultraviolet light (UV) by an LED type ultraviolet curing device or the like to be exposed and cured, thereby suppressing the adverse effect of heat distortion caused by heat rays. Furthermore, since the ultraviolet curable resin composition has delayed curing properties, it maintains a low viscosity state for a certain period after UV irradiation, and then rapidly increases in viscosity and cures. Therefore, since it can be combined with an adherend such as an electronic component after UV irradiation, the electronic component is not deteriorated by UV. In addition, it exhibits excellent adhesion to various types of substrates such as metal, glass and plastic.
  • the ultraviolet curable resin composition does not contain a conventional delayed curing agent, it is excellent in transparency and physical properties. Therefore, it is suitable for applications such as adhesives for various optical components that require miniaturization, high precision, and transparency, and sealing materials for organic EL elements.
  • an ultraviolet curable resin composition is applied to the substrate on which the organic EL elements are not attached, and the element side is subjected to UV irradiation. Bond and align with the substrate (adjustable due to low viscosity at this time). This makes it possible to avoid damage caused by UV and heat.
  • the ultraviolet curable resin composition according to the present embodiment can provide a necessary and sufficient delay time for alignment.
  • a dark part may be formed and an uncured part may be generated. It is difficult to occur with a curable resin composition.
  • the ultraviolet curable resin composition is in a liquid state immediately after irradiation with active energy rays and exhibits delayed curability that cures after a certain period of time. If such an ultraviolet curable resin composition is an adhesive, a delayed curable adhesive can be obtained.
  • the delayed-curing type adhesive here refers to an adhesive having a time allowance for bonding the members together by maintaining the liquid state for a certain period of time after applying the energy necessary to start the curing reaction (ie, usable adhesive). A long-time adhesive).
  • the delayed-curing adhesive refers to an adhesive that undergoes a curing reaction sufficiently to complete curing without additionally applying energy such as light or heat after bonding.
  • the delayed-curing adhesive is activated only when irradiated with active energy rays, and a curing reaction is started. Therefore, it hardly cures if it is not irradiated with active energy rays, and is different from an adhesive that spontaneously cures in a normal environment, such as a solvent-type adhesive and a cyanoacrylate instantaneous adhesive.
  • the delay time varies depending on the composition of the ultraviolet curable resin composition, the irradiation intensity of active energy rays, the temperature of the ultraviolet curable resin composition, and the like.
  • an active energy ray having a wavelength of 365 nm is irradiated with an irradiation dose of 50 mJ / cm 2 or more in an atmosphere at a temperature of 25 ° C.
  • the laminate 300 is manufactured using the ultraviolet curable resin composition as an adhesive.
  • an adhesive placement process, an irradiation process, an alignment process, a bonding process, and a curing process are sequentially performed.
  • an adhesive (uncured ultraviolet curable resin composition) 321 is placed on one side of the first plate 30.
  • the adhesive 321 is disposed in an amount of 30 g / m 2 or more and 1500 g / m 2 or less. Further, the adhesive 321 may be evenly arranged on the entire surface of the first plate 30, or may be arranged in a linear shape or a lattice shape.
  • the adhesive 321 may have the same degree of transparency as the fixed layer 32 after curing, or may be translucent or opaque.
  • the active energy ray 40 including ultraviolet rays is irradiated to the uncured adhesive 321 disposed on the first plate 30 after the adhesive placement step.
  • the active energy ray 40 may contain visible light or the like in addition to ultraviolet rays.
  • the adhesive 321 is cured by photocationic polymerization.
  • the irradiation step irradiates the active energy ray 40 in an amount necessary for the adhesive 321 to cure to the fixed layer 32.
  • an illumination device 41 such as an ultraviolet lamp is used for irradiation with the active energy ray 40.
  • the dose of the active energy ray 40 for example, be a 50 mJ / cm 2 or more 3000 mJ / cm 2 or less.
  • the first plate 30 and the second plate 31 are arranged at predetermined positions after the irradiation step.
  • the 1st board 30 is arrange
  • the surface of the first plate 30 on which the adhesive 321 is disposed is made to face one surface of the second plate 31.
  • the first plate 30 and the second plate 31 are stacked and bonded via an uncured adhesive 321 after the positioning step.
  • the adhesive 321 when the adhesive 321 is applied linearly, the adhesive 321 spreads between the first plate 30 and the second plate 31 so as to have a substantially uniform thickness due to the pressure at the time of bonding.
  • the uncured adhesive 321 is cured to form the fixed layer 32, and the first plate 30 and the second plate 31 are bonded by the fixed layer 32. .
  • Curing of the adhesive 321 in the curing process is performed by the active energy rays 40 irradiated in the irradiation process. Therefore, there is almost no need to irradiate the active energy ray 40 in the curing process. Even when the first plate 30 and the second plate 31 do not transmit ultraviolet rays, the curing of the adhesive 321 proceeds.
  • an uncured portion due to insufficient ultraviolet irradiation is less likely to occur in the fixed layer 32, and the adhesion strength between the fixed layers 32 (between the first plate 30 and the second plate 31) can be increased. it can.
  • the uncured adhesive 321 is less likely to ooze out between the first plate 30 and the second plate 31 and contaminates the periphery of the laminate 300. It becomes difficult.
  • the adhesive 321 used in the method for manufacturing the laminate 300 as described above is cured by the active energy ray 40 and is in a liquid or semi-cured state from the adhesive placement step to immediately after the bonding step.
  • This is a delayed-curing type adhesive that is completely cured at the end and has transparency after curing. Therefore, in the manufacturing method of the laminated body 300, the adhesive (uncured ultraviolet curable resin composition) 321 is bonded to the first plate 30 and the second plate 31 so that they can be reworked until just before the end of the bonding step. It is matched.
  • “rework” means that the first plate and the second plate are bonded together with an ultraviolet curable resin interposed therebetween, and then the first plate and the second plate are peeled off and reused.
  • Rework refers to adjusting the alignment of the first plate and the second plate by shifting the positions of the first plate and the second plate after the UV curable resin is interposed therebetween. means.
  • the reworkable UV curable resin is in a state before being completely cured (before becoming a fixed layer).
  • A Multifunctional epoxy compound (A1) Bifunctional polybutadiene epoxy resin ("R-45EPT", manufactured by Nagase ChemteX Corporation, does not fall under the aromatic benzene ring-containing epoxy compound) (A2) Bisphenol A type bifunctional epoxy resin (“YD-8125”, manufactured by Nippon Steel Chemical Co., Ltd., applicable to aromatic benzene ring-containing epoxy compounds) (B) Monofunctional epoxy compound (B1) Mixture of monofunctional epoxy resin having 11 to 15 carbon atoms (Licar Resin L-200, manufactured by Shin Nippon Rika Co., Ltd., does not correspond to an aromatic benzene ring-containing epoxy compound) (B2) A monofunctional epoxy compound containing an aromatic benzene ring (Denacol EX-141, manufactured by Nagase ChemteX Corporation) (B3) A monofunctional epoxy compound that is not a monofunctional epoxy compound having a long-chain hydrocarbon skeleton and is not an aromatic benzene ring-containing epoxy compound (Denacol
  • the laminate used a transparent plate as the first plate and a display plate as the second plate.
  • the first plate was a polycarbonate transparent plate having a long side length of 140 mm, a short side length of 80 mm, and a thickness of 1 mm. The first plate did not transmit ultraviolet light, and the total light transmittance was 95%.
  • the second plate was a liquid crystal panel having a long side length of 130 mm, a short side length of 75 mm, and a thickness of 0.4 mm. The second plate did not transmit ultraviolet light.
  • the 1st board and the 2nd board are bonded and fixed with the fixed layer which consists of a hardened material of the above-mentioned ultraviolet curable resin composition, and the 1st board and the 2nd board are arranged in parallel Manufactured.
  • an adhesive placement process In manufacturing the laminate, an adhesive placement process, an irradiation process, an alignment process, a bonding process, and a curing process were sequentially performed.
  • an uncured ultraviolet curable resin composition was applied as an adhesive in a grid pattern on one side of the first plate.
  • the amount of adhesive applied was 100 g / m 2 .
  • the adhesive applied to one side of the first plate was irradiated with ultraviolet rays.
  • a UV light source a UV-LED light source (Hamamatsu Photonics Co., Ltd., LC-L2, center wavelength 365 nm) is used, and UV light is irradiated at an illuminance of 100 mW / cm 2 for 5 seconds, for a total irradiation amount of 500 mJ / cm 2 . It was.
  • the first plate after the irradiation step was placed above the second plate to align the first plate and the second plate.
  • the first plate and the second plate were arranged in parallel so that the adhesive application surface of the first plate and the upper surface of the second plate face each other.
  • the first plate and the second plate were overlapped and bonded via an uncured adhesive.
  • the adhesive spread so as to have a substantially uniform thickness between the first plate and the second plate due to the pressure at the time of bonding.
  • the bonded first plate and second plate were allowed to stand to completely cure the adhesive.
  • Total light transmittance The evaluation method of the total light transmittance of the fixed layer was measured with a haze meter (NDH 4000, manufactured by Nippon Denshoku Industries Co., Ltd.), and 90% or more was marked as ⁇ , and less than 90% as x.
  • the thickness of the fixed layer is evaluated by measuring the thickness of the laminate with a dial thickness gauge (manufactured by Mitutoyo Corporation) and subtracting the thicknesses of the first and second plates. Was marked as x.
  • Adhesion (adhesion strength) The adhesive strength of each photocationic polymerization composition described in Table 1 was measured by a push-out method. It is coated on ABS resin plate A in a 40 mm square frame with a line width of 0.5 mm, and UV light is 100 mW / cm 2 using a UV-LED light source (Hamamatsu Photonics, LC-L2, center wavelength 365 nm). For 5 seconds. Immediately thereafter, an ABS resin plate B having a 20 mm ⁇ hole in the center was bonded to the ABS resin plate A, and cured for 12 hours in an atmosphere at room temperature of 25 ° C. to prepare a test piece.
  • the measurement part of the push-pull gauge is pressed against the ABS resin plate A through the hole of the ABS resin plate B, a vertical force is applied to the ABS resin plate A, and the maximum stress until peeling is measured to obtain the adhesive strength. .
  • the test speed was 10 mm / sec.
  • the required adhesive strength varies depending on the application. Here, it is 40N (1.0 MPa) or more, 60N or more is indicated by ⁇ , 40N or more and less than 60N is indicated by ⁇ , and 40N or less is indicated by ⁇ .
  • the storage elastic modulus of the fixed layer was evaluated by pouring each of the cationic photopolymerization compositions shown in Table 1 into a silicone rubber having a diameter of 20 mm and a thickness of 1 mm, and using an UV-LED light source to emit ultraviolet light at 100 mW / A solid material produced by irradiation for 5 seconds at an illuminance of cm 2 was measured using a rheometer in an oscillation mode at 25 ° C. and 1 Hz.
  • As the UV-LED light source LC-L2 manufactured by Hamamatsu Photonics Co., Ltd., center wavelength 365 nm was used.
  • the rheometer used was AR2000ex, manufactured by TA Instruments.
  • the required storage elastic modulus varies depending on the application and structure, but here, 0.1 MPa or less is marked with ⁇ , and larger is marked with ⁇ .
  • each photocationic polymerization composition described in Table 1 can be removed from the surface layer of the second plate with bamboo skewers and alcoholic solvents. It was carried out whether or not. Those in which the cationic photopolymerization composition could be removed were marked with ⁇ , and those that could not be made were marked with x.
  • the laminate was put into a constant temperature bath at 80 ° C. for 250 hours, and the discoloration of the fixed layer of each photocationic polymerization composition described in Table 1 was visually confirmed.
  • the fixed layer was visually confirmed, and those that did not change from the initial stage were marked with ⁇ , and those that changed from the initial stage and yellowed were marked with ⁇ .
  • the delay time was measured using the change in viscosity after UV irradiation at room temperature and 25 ° C.
  • a UV irradiation type rheometer manufactured by Anton Paar Japan Co., Ltd., MCR-100 was used to measure the viscosity of each of the photocationic polymerization compositions of Examples and Comparative Examples before ultraviolet irradiation and changes in viscosity after irradiation.
  • the delay time was defined as the time from immediately after the start of ultraviolet irradiation to the liquid photocationic polymerization composition until the viscosity of the photocationic polymerization composition reached 50000 Pa ⁇ s. This is because the fluidity is almost lost and the viscosity at which bonding becomes impossible is about 50000 Pa ⁇ s. If this delay time is 15 seconds or less, there is little time for pasting, and if it is 60 minutes or more, there is a high possibility that the member will be displaced.
  • Heat cycle resistance In the evaluation method of heat cycle resistance, the laminate was put into a heat cycle tank where -40 ° C. for 30 minutes and 80 ° C. for 30 minutes were alternately repeated. And when the above-mentioned temperature cycle was made into 1 cycle, it was confirmed whether the 1st board, the 2nd board, and the fixed layer had peeled in the laminated body after 100 cycles progress. The case where peeling did not occur was marked with ⁇ , and the case where peeling occurred was marked with ⁇ .
  • This embodiment has the following features.
  • the ultraviolet curable resin composition of the present embodiment includes a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound.
  • the ultraviolet curable resin composition contains the polyfunctional epoxy compound and the polyfunctional oxetane compound with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound.
  • the total amount is 30 parts by mass or more and 95 parts by mass or less
  • the monofunctional epoxy compound is contained by 70 parts by mass or less and 5 parts by mass or more.
  • the monofunctional epoxy compound contains a monofunctional epoxy compound having a hydrocarbon skeleton having 7 to 20 carbon atoms.
  • At least one of the polyfunctional epoxy compound and the monofunctional epoxy compound contains an aromatic benzene ring-containing epoxy compound.
  • Content of the said aromatic benzene ring containing epoxy compound is 1 to 40 mass parts with respect to 100 mass parts of total amounts of the said polyfunctional epoxy compound, the said monofunctional epoxy compound, and the said polyfunctional oxetane compound. .
  • the adherend When the adherend is bonded with a cured product of the above-described ultraviolet curable resin composition, the adhesion strength between the layers of the laminate is high, and the rework and antifouling properties during the production of the laminate are excellent.
  • the ultraviolet curable resin composition of the present embodiment preferably further contains an elastomer.
  • the polar group in the elastomer strengthens the chemical interaction with the adherend, or the cationically polymerizable substituent in the elastomer Changes in chemical properties such as formation of chemical bonds with the adherend occur, and adhesion (adhesive strength) between the cured product of the ultraviolet curable resin composition and the adherend is improved.
  • the laminated body (300) of this embodiment includes a first plate (30) that does not transmit ultraviolet light, a second plate (31) that does not transmit ultraviolet light, and a space between the first plate (30) and the second plate (31). And a laminated body (300) having a fixed layer (32) for fixing the first plate (30) and the second plate (31).
  • the fixing layer (32) is an ultraviolet curable resin provided between the first plate (30) and the second plate (31) to bond the first plate (30) and the second plate (31) so that they can be reworked. It is a cured product of the composition.
  • the ultraviolet curable resin composition includes a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound.
  • the total content of the polyfunctional epoxy compound and the polyfunctional oxetane compound is 100 parts by mass or more with respect to 100 parts by mass of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound.
  • the amount of the monofunctional epoxy compound is 70 parts by mass or less and 5 parts by mass or more.
  • the monofunctional epoxy compound contains a monofunctional epoxy compound having a hydrocarbon skeleton having 7 to 20 carbon atoms.
  • At least one of the polyfunctional epoxy compound and the monofunctional epoxy compound contains an aromatic benzene ring-containing epoxy compound. Content of the said aromatic benzene ring containing epoxy compound is 1 to 40 mass parts with respect to 100 mass parts of total amounts of the said polyfunctional epoxy compound, the said monofunctional epoxy compound, and the said polyfunctional oxetane compound. .
  • the adhesion strength between the first plate (30) and the second plate (31) by the fixed layer (32) is high, and rework and antifouling properties when the first plate (30) and the second plate (31) are bonded. Excellent.
  • the first plate (30) is a transparent plate having a total light transmittance of 85% or more, and the second plate (31) is provided in parallel to the first plate (30).
  • a display board is preferred.
  • this laminated body is a display device of a portable electronic terminal such as a smartphone or a mobile phone
  • the first plate (30) and the second plate (31) with the fixed layer (32) have high adhesion strength, and the first plate It is excellent in rework and antifouling property when adhering (30) and the second plate (31).
  • the total light transmittance of the fixed layer (32) is 85% or more.
  • this laminate is a display device of a portable electronic terminal such as a smartphone or a mobile phone, the visibility of display of characters, images and the like is not easily impaired by the fixed layer (32).
  • the thickness of the fixed layer (32) is 10 ⁇ m or more and 10 mm or less.
  • this laminate is a display device of a portable electronic terminal such as a smartphone or a mobile phone, it is difficult to be thick and the portability is not easily lost.
  • this laminate is a display device of a portable electronic terminal such as a smartphone or a mobile phone
  • the first plate (30) and the second plate (31) are hardly detached due to an impact caused by dropping or the like.
  • the adhesive strength between the fixed layer (32) and the second plate (31) is 10 N / cm 2 or more and 150 N / cm 2 or less.
  • the second plate (31) can be easily removed from the fixed layer (32), which is excellent for rework.

Abstract

The present invention addresses the problem of providing an ultraviolet-curable resin composition that has high interlayer adhesion strength and exhibits superior reworkability and antifouling properties during production process. This resin composition comprises a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound. The contained amount of the total of the polyfunctional epoxy compound and the polyfunctional oxetane compound is 30-95 parts by mass with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. The monofunctional epoxy compound is contained in an amount of 70-5 parts by mass. The monofunctional epoxy compound includes a monofunctional epoxy compound with a hydrocarbon skeleton having 7-20 carbon atoms. An aromatic benzene ring-containing epoxy compound is contained in an amount of 1-40 parts by mass.

Description

紫外線硬化性樹脂組成物及び積層体Ultraviolet curable resin composition and laminate
　本発明は紫外線硬化性樹脂組成物及び積層体に関する。詳しくは、本発明は、表示装置などとして利用される積層体及びこれに用いる紫外線硬化性樹脂組成物に関する。 The present invention relates to an ultraviolet curable resin composition and a laminate. In detail, this invention relates to the laminated body utilized as a display apparatus etc., and the ultraviolet curable resin composition used for this.
　従来、スマートフォン、携帯電話などの携帯用電子端末の表示装置として、透明板と表示板とを備えた積層体が提案されている。透明板は表示板をカバーして保護する機能を有し、プラスチック板又はガラス板などが用いられている。表示板は文字及び画像などを表示する機能を有し、液晶パネル又は有機ＥＬパネルなどが用いられている。このような積層体を製造するにあたっては、透明粘着剤で透明板と表示板とを貼り合わせて固定するようにしている。 Conventionally, a laminate including a transparent plate and a display plate has been proposed as a display device for portable electronic terminals such as smartphones and mobile phones. The transparent plate has a function of covering and protecting the display plate, and a plastic plate or a glass plate is used. The display board has a function of displaying characters and images, and a liquid crystal panel or an organic EL panel is used. In manufacturing such a laminate, the transparent plate and the display plate are bonded and fixed with a transparent adhesive.
　透明粘着剤としては、ＯＣＡ（Ｏｐｔｉｃａｌ　Ｃｌｅａｒ　Ａｄｈｅｓｉｖｅ）又は熱エネルギーによらず紫外線（ＵＶ）で硬化する紫外線硬化性樹脂組成物であるＯＣＲ（Ｏｐｔｉｃａｌ　Ｃｌｅａｒ　Ｒｅｓｉｎ）が広く用いられている。このようなＯＣＡ又はＯＣＲは、ＬＣＤ（Ｌｉｑｕｉｄ　Ｃｒｙｓｔａｌ　Ｄｉｓｐｌａｙ）又はＯＬＥＤ（Ｏｒｇａｎｉｃ　Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）等に用いられるディスプレイ封止材として好ましく用いられている。 As the transparent adhesive, OCA (Optical Clear Adhesive) or OCR (Optical Clear Resin), which is an ultraviolet curable resin composition that is cured by ultraviolet rays (UV) regardless of thermal energy, is widely used. Such OCA or OCR is preferably used as a display sealing material used for LCD (Liquid Crystal Display) or OLED (Organic Light Emitting Diode).
　図３Ａ～図３Ｃは、ＯＣＡを用いた積層体の製造工程を示している。図３Ａでは、透明板１０の片面にフィルムのＯＣＡ１１をローラー１２で押し付けて密着している。図３Ｂでは、透明板１０にラミネートしたＯＣＡ１１の表面を表示板１３の片面にローラー１４で押し付けて密着している。このようにして透明板１０と表示板１３とがＯＣＡ１１により接着されて固定された積層体１００を得ることができる（図３Ｃ）。 3A to 3C show a manufacturing process of a laminate using OCA. In FIG. 3A, the OCA 11 of the film is pressed and adhered to one side of the transparent plate 10 with a roller 12. In FIG. 3B, the surface of the OCA 11 laminated on the transparent plate 10 is pressed and adhered to one side of the display plate 13 with a roller 14. In this way, the laminate 100 in which the transparent plate 10 and the display plate 13 are bonded and fixed by the OCA 11 can be obtained (FIG. 3C).
　図４Ａ～図４Ｅは、ＯＣＲを用いた積層体の製造工程を示している。図４Ａでは、透明板２０の片面に液状のＯＣＲ２１を塗布している。図４Ｂでは、透明板２０のＯＣＲ２１を塗布した片面を表示板２３の片面に対向させ、透明板２０と表示板２３とをアライメント（位置合わせ）している。図４Ｃでは、透明板２０と表示板２３とを重ね合わせている。図４Ｄでは、ＵＶ照射装置２５から発せられたＵＶを透明板２０に照射し、透明板２０を通過したＵＶが透明板２０と表示板２３の間にあるＯＣＲ２１に照射される。これにより、ＯＣＲ２１が硬化するとともに、硬化したＯＣＲ２１で透明板２０と表示板２３が接着される。このようにして透明板２０と表示板２３とが硬化したＯＣＲ２１により接着されて固定された積層体２００を得ることができる（図４Ｅ）。 4A to 4E show a manufacturing process of a laminated body using OCR. In FIG. 4A, liquid OCR 21 is applied to one side of the transparent plate 20. In FIG. 4B, the transparent plate 20 and the display plate 23 are aligned (positioned) with one side of the transparent plate 20 coated with the OCR 21 facing the one side of the display plate 23. In FIG. 4C, the transparent plate 20 and the display plate 23 are overlapped. In FIG. 4D, the UV emitted from the UV irradiation device 25 is applied to the transparent plate 20, and the UV that has passed through the transparent plate 20 is applied to the OCR 21 between the transparent plate 20 and the display plate 23. Thereby, the OCR 21 is cured, and the transparent plate 20 and the display plate 23 are bonded by the cured OCR 21. In this way, it is possible to obtain a laminate 200 in which the transparent plate 20 and the display plate 23 are bonded and fixed by the cured OCR 21 (FIG. 4E).
　また、プレキュアＯＣＲを用いた貼り合わせ工程も提案されている（特許文献１参照）。特許文献１に記載された内容は、透明板の片面に液状のＯＣＲを塗布した後、透明板と表示板とを重ね合わせる前に、ＯＣＲにＵＶ照射して半硬化状態にし、その後に透明板と表示板の貼り合わせを実施するという技術である。 Also, a bonding process using precure OCR has been proposed (see Patent Document 1). The content described in Patent Document 1 is that after applying a liquid OCR on one side of a transparent plate, before superimposing the transparent plate and the display plate, UV irradiation is applied to the OCR to make it semi-cured, and then the transparent plate This is a technique of bonding the display boards.
　ところが、ＯＣＡを用いた貼り合わせ工程では、透明板と表示板の接着面に段差があった場合に、その段差を無くすようにＯＣＡを配置することが困難であり、段差の周辺部分において透明板と表示板の密着強度（接着強度）が低下することがあった。また、透明板と表示板とを一旦貼り合わせてしまうと、透明板と表示板の位置ずれを修正しにくく、しかも透明板と表示板とを再利用可能な状態で剥がすことも困難であり、リワーク性が低いという問題があった。 However, in the bonding process using OCA, when there is a step on the bonding surface of the transparent plate and the display plate, it is difficult to dispose the OCA so as to eliminate the step, and the transparent plate is formed around the step. The adhesion strength (adhesion strength) of the display board may be reduced. Moreover, once the transparent plate and the display plate are pasted together, it is difficult to correct the misalignment between the transparent plate and the display plate, and it is also difficult to peel the transparent plate and the display plate in a reusable state. There was a problem that reworkability was low.
　また、ＯＣＲを用いた貼り合わせ工程では、ＵＶが透過して照射可能である箇所はＯＣＲが硬化する。しかし、ＵＶが透過せずに照射できない箇所は硬化せず、透明板と表示板の密着強度が低下したり、場合によっては未硬化のＯＣＲが貼り合せた積層体から染み出て積層体の周囲を汚染したりするという問題があった。 Also, in the bonding process using OCR, the OCR is cured at a portion where UV can be transmitted and irradiated. However, the part that cannot be irradiated without UV transmission is not cured, the adhesion strength between the transparent plate and the display panel is reduced, or in some cases, the uncured OCR sticks out of the laminate and the periphery of the laminate There was a problem of polluting.
　さらに、特許文献１に記載されているようなプレキュアＯＣＲでは一般的なＯＣＲと比較して密着強度が低下する場合があった。 Furthermore, in the case of the precure OCR described in Patent Document 1, the adhesion strength may be reduced as compared with a general OCR.
特開２０１３－２３５１５３号公報JP 2013-235153 A
　本発明は上記の点に鑑みてなされたものであり、積層体の層間の密着強度が高く、積層体の製造時のリワーク及び防汚性に優れる紫外線硬化性樹脂組成物及びこれを用いた積層体を提供することを目的とするものである。 The present invention has been made in view of the above points, and has a high adhesion strength between layers of a laminate, an ultraviolet curable resin composition excellent in rework and antifouling properties at the time of producing the laminate, and a laminate using the same. The purpose is to provide a body.
　本発明に係る紫外線硬化性樹脂組成物は、
　多官能エポキシ化合物と、単官能エポキシ化合物と、多官能オキセタン化合物とを含み、
　前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して、前記多官能エポキシ化合物及び前記多官能オキセタン化合物の含有量が合計で３０質量部以上９５質量部以下であり、前記単官能エポキシ化合物を７０質量部以下５質量部以上含有し、
　前記単官能エポキシ化合物は、炭素数７以上２０以下の炭化水素骨格の単官能エポキシ化合物を含有し、
　前記多官能エポキシ化合物及び前記単官能エポキシ化合物の少なくとも一方は、芳香族ベンゼン環含有エポキシ化合物を含有し、
　前記芳香族ベンゼン環含有エポキシ化合物の含有量は、前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して１質量部以上４０質量部以下である。 The ultraviolet curable resin composition according to the present invention is:
A polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound;
The total content of the polyfunctional epoxy compound and the polyfunctional oxetane compound is 100 parts by mass or more with respect to 100 parts by mass of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. The amount of the monofunctional epoxy compound is 70 parts by mass or less and 5 parts by mass or more.
The monofunctional epoxy compound contains a monofunctional epoxy compound having a hydrocarbon skeleton having 7 to 20 carbon atoms,
At least one of the polyfunctional epoxy compound and the monofunctional epoxy compound contains an aromatic benzene ring-containing epoxy compound,
Content of the said aromatic benzene ring containing epoxy compound is 1 to 40 mass parts with respect to 100 mass parts of total amounts of the said polyfunctional epoxy compound, the said monofunctional epoxy compound, and the said polyfunctional oxetane compound. .
　本発明に係る積層体は、
　紫外線を透過しない第１板と、
　紫外線を透過しない第２板と、
　前記第１板と前記第２板と間に設けられ、前記第１板と前記第２板とを固定する固定層とを有する積層体であって、
　前記固定層は、前記第１板と前記第２板の間に設けられて前記第１板と前記第２板とをリワーク可能に貼り合わせる紫外線硬化性樹脂組成物の硬化物であり、
　前記紫外線硬化性樹脂組成物は、多官能エポキシ化合物と、単官能エポキシ化合物と、多官能オキセタン化合物とを含み、前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して、前記多官能エポキシ化合物及び前記多官能オキセタン化合物の含有量が合計で３０質量部以上９５質量部以下であり、前記単官能エポキシ化合物を７０質量部以下５質量部以上含有し、
　前記単官能エポキシ化合物は、炭素数７以上２０以下の炭化水素骨格の単官能エポキシ化合物を含有し、
　前記多官能エポキシ化合物及び前記単官能エポキシ化合物の少なくとも一方は、芳香族ベンゼン環含有エポキシ化合物を含有し、
　前記芳香族ベンゼン環含有エポキシ化合物の含有量は、前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して、１質量部以上４０質量部以下である。 The laminate according to the present invention is
A first plate that does not transmit ultraviolet light;
A second plate that does not transmit ultraviolet light;
A laminated body provided between the first plate and the second plate and having a fixing layer for fixing the first plate and the second plate;
The fixed layer is a cured product of an ultraviolet curable resin composition that is provided between the first plate and the second plate and bonds the first plate and the second plate so that they can be reworked,
The ultraviolet curable resin composition includes a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound, and a total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. The total content of the polyfunctional epoxy compound and the polyfunctional oxetane compound is 30 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass, and the monofunctional epoxy compound contains 70 parts by mass or less and 5 parts by mass or more. And
The monofunctional epoxy compound contains a monofunctional epoxy compound having a hydrocarbon skeleton having 7 to 20 carbon atoms,
At least one of the polyfunctional epoxy compound and the monofunctional epoxy compound contains an aromatic benzene ring-containing epoxy compound,
The content of the aromatic benzene ring-containing epoxy compound is 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. is there.
図１Ａは本発明に係る一実施の形態を示す概略の分解斜視図である。図１Ｂは本発明に係る一実施の形態を示す概略の断面図である。FIG. 1A is a schematic exploded perspective view showing an embodiment according to the present invention. FIG. 1B is a schematic sectional view showing an embodiment according to the present invention. 図２Ａは本発明に係る一実施の形態の製造方法において、接着剤配置工程を示す概略の斜視図である。図２Ｂは本発明に係る一実施の形態の製造方法において、照射工程を示す概略の斜視図である。図２Ｃは本発明に係る一実施の形態の製造方法において、位置合わせ工程を示す概略の斜視図である。図２Ｄは本発明に係る一実施の形態の製造方法において、貼り合わせ工程を示す概略の斜視図である。図２Ｅは本発明に係る一実施の形態の製造方法において、養生工程を示す概略の斜視図である。FIG. 2A is a schematic perspective view showing an adhesive placement step in the manufacturing method of one embodiment according to the present invention. FIG. 2B is a schematic perspective view showing an irradiation step in the manufacturing method of one embodiment according to the present invention. FIG. 2C is a schematic perspective view showing an alignment process in the manufacturing method according to the embodiment of the present invention. FIG. 2D is a schematic perspective view showing a bonding step in the manufacturing method according to the embodiment of the present invention. FIG. 2E is a schematic perspective view showing a curing process in the manufacturing method according to the embodiment of the present invention. 図３Ａ～図３Ｃは従来の積層体の製造工程を示す概略の斜視図である。3A to 3C are schematic perspective views showing a manufacturing process of a conventional laminate. 図４Ａ～図４Ｅは従来の積層体の製造工程を示す概略の斜視図である。4A to 4E are schematic perspective views showing a manufacturing process of a conventional laminate.
　以下、本発明を実施するための形態を説明する。 Hereinafter, modes for carrying out the present invention will be described.
　（積層体）
　図１Ａ及び図１Ｂは積層体３００を示している。積層体３００は、第１板３０と第２板３１と固定層３２とが層状に重なって形成されている。積層体３００は、例えば、スマートフォン及び携帯電話などの携帯用電子端末の表示装置として形成されており、この場合、第１板３０は透明板３０１として形成され、第２板３１は表示板３１１として形成されている。固定層３２は紫外線硬化性樹脂組成物の硬化物で形成されている。図１Ｂにおいて、符号３３は加飾印刷層である。 (Laminate)
1A and 1B show a laminate 300. FIG. The laminated body 300 is formed by layering the first plate 30, the second plate 31, and the fixed layer 32. The laminated body 300 is formed as a display device for portable electronic terminals such as smartphones and mobile phones, for example. In this case, the first plate 30 is formed as a transparent plate 301 and the second plate 31 is used as a display plate 311. Is formed. The fixed layer 32 is formed of a cured product of an ultraviolet curable resin composition. In FIG. 1B, the code | symbol 33 is a decoration printing layer.
　透明板３０１は表示板３１１をカバーして保護する機能を有し、ポリカーボネート及びアクリル樹脂製などのプラスチック板又はガラス板などが用いられている。表示板３１１は文字及び画像などを表示する機能を有し、液晶パネルディスプレイ又は有機ＥＬパネルディスプレイなどが用いられている。例えば、バックライト３１２と液晶パネル３１３とカラーフィルター３１４とを備えた表示板３１１を例示することができる。固定層３２は第１板３０と第２板３１との間に設けられ、第１板３０と第２板３１とを接着して固定している。第１板３０と第２板３１は固定層３２により互いに位置ずれしないように形成され、また互いに容易に剥離しないように形成されている。第１板３０と第２板３１とは互いに平行となるように配置されている。なお、第１板３０と第２板３１とは厳密に平行である必要がなく、実質的に平行と見なせる範囲で良い。 The transparent plate 301 has a function of covering and protecting the display plate 311, and a plastic plate or glass plate made of polycarbonate or acrylic resin is used. The display plate 311 has a function of displaying characters and images, and a liquid crystal panel display, an organic EL panel display, or the like is used. For example, a display plate 311 including a backlight 312, a liquid crystal panel 313, and a color filter 314 can be exemplified. The fixed layer 32 is provided between the first plate 30 and the second plate 31 and adheres and fixes the first plate 30 and the second plate 31. The first plate 30 and the second plate 31 are formed by the fixed layer 32 so as not to be displaced from each other, and are formed so as not to be easily separated from each other. The first plate 30 and the second plate 31 are arranged so as to be parallel to each other. The first plate 30 and the second plate 31 do not have to be strictly parallel, and may be within a range that can be regarded as being substantially parallel.
　第１板３０と第２板３１とは紫外線を透過しない。ここで「紫外線を透過しない」とは、紫外線の透過率が０％以上５％以下であることを意味する。また透明板３０１は全光透過率が８５％以上１００％以下であることが好ましく、これにより、表示板３１１で表示された文字及び画像などが透明板３０１を透して視認しやすい。 The first plate 30 and the second plate 31 do not transmit ultraviolet rays. Here, “does not transmit ultraviolet rays” means that the transmittance of ultraviolet rays is 0% or more and 5% or less. In addition, the transparent plate 301 preferably has a total light transmittance of 85% or more and 100% or less, so that characters and images displayed on the display plate 311 are easily visible through the transparent plate 301.
　固定層３２は全光透過率が８５％以上１００％以下であることが好ましく、これにより、表示板３１１で表示された文字及び画像などが透明板３０１及び固定層３２を透して視認しやすい。固定層３２は厚みが１０μｍ以上１０ｍｍ以下であることが好ましく、これにより、固定層３２が破壊しにくくなり、第１板３０と第２板３１とを強固に固定することが可能となる。また固定層３２は温度２０℃における貯蔵弾性率が０．００１ＭＰａ以上０．１ＭＰａ以下であることが好ましく、これにより、第１板３０と第２板３１とを強固に固定しやすくなり、第１板３０と第２板３１の剥離及び位置ずれを防止しやすくなる。さらに固定層３２は第２板３１との密着強度（接着強度）が１０Ｎ／ｃｍ２以上１５０Ｎ／ｃｍ２以下であることが好ましく、これにより、第１板３０と第２板３１とを強固に固定しやすくなり、第１板３０と第２板３１の剥離及び位置ずれを防止しやすくなる。 The fixed layer 32 preferably has a total light transmittance of 85% or more and 100% or less, so that characters and images displayed on the display plate 311 can be easily seen through the transparent plate 301 and the fixed layer 32. . The fixing layer 32 preferably has a thickness of 10 μm or more and 10 mm or less. This makes it difficult for the fixing layer 32 to break, and allows the first plate 30 and the second plate 31 to be firmly fixed. The fixed layer 32 preferably has a storage elastic modulus at a temperature of 20 ° C. of 0.001 MPa or more and 0.1 MPa or less. This makes it easy to firmly fix the first plate 30 and the second plate 31 to each other. It becomes easy to prevent the separation and displacement of the plate 30 and the second plate 31. Further, the fixing layer 32 preferably has an adhesion strength (adhesive strength) with the second plate 31 of 10 N / cm 2 or more and 150 N / cm 2 or less, thereby strengthening the first plate 30 and the second plate 31. It becomes easy to fix, and it becomes easy to prevent peeling and misalignment of the first plate 30 and the second plate 31.
　（紫外線硬化性樹脂組成物）
　紫外線硬化性樹脂組成物は紫外線が照射されることにより硬化するものであり、硬化により固定層３２を形成するものである。紫外線硬化性樹脂組成物は、少なくとも、多官能エポキシ化合物と、単官能エポキシ化合物と、多官能オキセタン化合物とを含んでいる。 (UV curable resin composition)
The ultraviolet curable resin composition cures when irradiated with ultraviolet rays, and forms the fixed layer 32 by curing. The ultraviolet curable resin composition contains at least a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound.
　（多官能エポキシ化合物）
　多官能エポキシ化合物としては、１分子中に２個以上のエポキシ基を有するものであれば特に限定はされず、固形状のものであっても液状のものであってもよい。具体的には、例えば、ポリブタジエンエポキシ樹脂、脂肪族エポキシ化合物、エポキシ変性シリコーン化合物、脂環式エポキシ化合物、水添ビスフェノールＡ型エポキシ化合物などのアルコール型エポキシ化合物、エポキシ化ポリブタジエン化合物、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂などのビスフェノール型エポキシ化合物、ナフタレン型エポキシ化合物、ビフェニル型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物等のノボラック型エポキシ化合物、エポキシ化スチレン－ブタジエン－スチレンブロック共重合体、グリシジルアミン型エポキシ化合物、異節環状型エポキシ化合物、多官能性エポキシ化合物、グリシジルエーテル型エポキシ化合物、グリシジルエステル型エポキシ化合物、臭素化エポキシ化合物等のハロゲン化エポキシ化合物、ゴム変成エポキシ化合物、ウレタン変成エポキシ化合物、エポキシ基含有ポリエステル化合物、エポキシ基含有ポリウレタン化合物、エポキシ基含有アクリル化合物等が挙げられる。 (Polyfunctional epoxy compound)
The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule, and may be solid or liquid. Specifically, for example, polybutadiene epoxy resin, aliphatic epoxy compound, epoxy-modified silicone compound, alicyclic epoxy compound, alcohol type epoxy compound such as hydrogenated bisphenol A type epoxy compound, epoxidized polybutadiene compound, bisphenol A type epoxy Resin, bisphenol type epoxy compound such as bisphenol F type epoxy resin, naphthalene type epoxy compound, biphenyl type epoxy compound, phenol novolac type epoxy compound, cresol novolak type epoxy compound and other novolak type epoxy compound, epoxidized styrene-butadiene-styrene block Copolymer, glycidylamine type epoxy compound, heterocyclic epoxy compound, multifunctional epoxy compound, glycidyl ether type epoxy compound, group Glycidyl ester type epoxy compounds, halogenated epoxy compounds such as brominated epoxy compound, a rubber modified epoxy compounds, urethane modified epoxy compound, an epoxy group-containing polyester compounds, epoxy group-containing polyurethane compound, an epoxy group-containing acrylic compounds.
　なかでも、光カチオン重合性がより高く、少ない光量でもより効率的に光硬化が進行することから、ビスフェノールＡ型エポキシ化合物、ナフタレン型エポキシ化合物、脂環式エポキシ化合物等を挙げることができる。これらの多官能エポキシ化合物は、単独で用いられてもよく、２種以上が併用されてもよい。 Among these, bisphenol A type epoxy compound, naphthalene type epoxy compound, alicyclic epoxy compound, and the like can be mentioned because photocationic polymerization is higher and photocuring proceeds more efficiently even with a small amount of light. These polyfunctional epoxy compounds may be used independently and 2 or more types may be used together.
　なお、硬化収縮応力が小さく、硬化物の被着体に対する密着力が高いという観点からは、上述した多官能エポキシ化合物の中でも、２官能エポキシ樹脂を用いることが好ましい。さらに、透湿性・吸湿性・温度依存性が低く、また熱応力が小さいために冷熱サイクルテストなどの信頼性試験に有効であるという観点からは、ポリブタジエンエポキシ樹脂等を用いることが好ましい。 In addition, it is preferable to use a bifunctional epoxy resin among the polyfunctional epoxy compounds mentioned above from the viewpoint that the curing shrinkage stress is small and the adhesion of the cured product to the adherend is high. Furthermore, it is preferable to use a polybutadiene epoxy resin or the like from the viewpoint of being effective in reliability tests such as a thermal cycle test because of its low moisture permeability, hygroscopicity, and temperature dependency and low thermal stress.
　（単官能エポキシ化合物）
　単官能エポキシ化合物は、１分子中に１個のエポキシ基を有するものであって、固形状のものであっても液状のものであってもよい。単官能エポキシ化合物は、少なくとも炭素数７以上２０以下の長鎖炭化水素骨格を有する単官能エポキシ化合物（以下、単に、長鎖単官能エポキシ化合物ともいう）を含有している。また単官能エポキシ化合物は長鎖単官能エポキシ化合物のみを含有していてもよい。このような長鎖単官能エポキシ化合物を用いることによって、従来のような遅延硬化剤を用いることなく、遅延硬化性を有する紫外線硬化性樹脂組成物を得ることができる。 (Monofunctional epoxy compound)
The monofunctional epoxy compound has one epoxy group in one molecule and may be solid or liquid. The monofunctional epoxy compound contains a monofunctional epoxy compound having a long chain hydrocarbon skeleton having at least 7 to 20 carbon atoms (hereinafter also simply referred to as a long chain monofunctional epoxy compound). Moreover, the monofunctional epoxy compound may contain only a long-chain monofunctional epoxy compound. By using such a long-chain monofunctional epoxy compound, an ultraviolet curable resin composition having delayed curing properties can be obtained without using a conventional delayed curing agent.
　長鎖炭化水素骨格を有する単官能エポキシ化合物は、鎖中もしくは鎖末端に１つのエポキシ基を有する炭素数７以上２０以下の炭化水素骨格の化合物であれば得に限定されない。例えば、１，２－エポキシドデカン、１，２－エポキシエイコサン、１，２－エポキシデカン、２－エチルヘキシルグリシジルエーテル、１，２－エポキシテトラデカン、１，２－エポキシヘキサデカン、グリシジルラウリルエーテル等が挙げられる。具体的には、例えば、三菱化学社の「ＹＥＤ１１１ＡＮ」、「ＹＥＤ１１１Ｎ」、「ＹＥＤ１８８」、新日本理化社の「リカレジン　Ｌ－２００」、ナガセケムテックス社の「ＥＸ－１２１」「ＥＸ－１９２」等を用いることができる。なかでも、粘度と遅延硬化性の調整しやすさの面から、炭素数１１以上１５以下の炭化水素骨格を有する単官能エポキシ化合物を用いることがより好ましい。 The monofunctional epoxy compound having a long-chain hydrocarbon skeleton is not particularly limited as long as it is a compound having a hydrocarbon skeleton having 7 to 20 carbon atoms and having one epoxy group in the chain or at the chain end. Examples include 1,2-epoxydodecane, 1,2-epoxyeicosane, 1,2-epoxydecane, 2-ethylhexyl glycidyl ether, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, glycidyl lauryl ether, and the like. It is done. Specifically, for example, “YED111AN”, “YED111N”, “YED188” from Mitsubishi Chemical Corporation, “Lika Resin L-200” from Shin Nippon Chemical Co., Ltd., “EX-121”, “EX-192” from Nagase ChemteX Corporation Etc. can be used. Among these, it is more preferable to use a monofunctional epoxy compound having a hydrocarbon skeleton having 11 to 15 carbon atoms from the viewpoint of easy adjustment of viscosity and delayed curing.
　（芳香族ベンゼン環含有エポキシ化合物）
　紫外線硬化性樹脂組成物は、芳香族ベンゼン環含有エポキシ化合物を含有している。芳香族ベンゼン環含有エポキシ化合物は、紫外線硬化性樹脂組成物の密着強度を向上する働きを有する一方で、高温状態で長期間曝されると分解して着色が発生するため、密着性と高温時の着色性を調整できると考えられる。芳香族ベンゼン環含有エポキシ化合物は、１分子中に１個以上のエポキシ基（環）を有するものであれば特に限定はされず、固形状のものであっても液状のものであってもよい。また芳香族ベンゼン環含有エポキシ化合物は、１分子中に１個以上の芳香族ベンゼン環を有するものであれば特に限定なく用いることができる。 (Aromatic benzene ring-containing epoxy compound)
The ultraviolet curable resin composition contains an aromatic benzene ring-containing epoxy compound. The aromatic benzene ring-containing epoxy compound has the function of improving the adhesive strength of the ultraviolet curable resin composition, but decomposes and develops color when exposed to a long period of time at high temperatures. It is thought that the colorability of the can be adjusted. The aromatic benzene ring-containing epoxy compound is not particularly limited as long as it has one or more epoxy groups (rings) in one molecule, and may be solid or liquid. . The aromatic benzene ring-containing epoxy compound can be used without particular limitation as long as it has one or more aromatic benzene rings in one molecule.
　紫外線硬化性樹脂組成物は、芳香族ベンゼン環含有エポキシ化合物を上記多官能エポキシ化合物の一部又は全部として含有することが可能である。この場合、芳香族ベンゼン環を含有する多官能エポキシ化合物としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂などのビスフェノール型エポキシ化合物、ナフタレン型エポキシ化合物、ビフェニル型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物等のノボラック型エポキシ化合物、エポキシ化スチレン－ブタジエン－スチレンブロック共重合体、グリシジルアミン型エポキシ化合物、異節環状型エポキシ化合物、多官能性エポキシ化合物、グリシジルエーテル型エポキシ化合物、グリシジルエステル型エポキシ化合物、臭素化エポキシ化合物等のハロゲン化エポキシ化合物、ゴム変成エポキシ化合物、ウレタン変成エポキシ化合物、エポキシ基含有ポリエステル化合物、エポキシ基含有ポリウレタン化合物、エポキシ基含有アクリル化合物等が挙げられる。 The ultraviolet curable resin composition can contain an aromatic benzene ring-containing epoxy compound as part or all of the polyfunctional epoxy compound. In this case, as the polyfunctional epoxy compound containing an aromatic benzene ring, bisphenol type epoxy compound such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, naphthalene type epoxy compound, biphenyl type epoxy compound, phenol novolac type epoxy compound , Novolac epoxy compounds such as cresol novolac epoxy compounds, epoxidized styrene-butadiene-styrene block copolymers, glycidylamine epoxy compounds, heterocyclic epoxy compounds, polyfunctional epoxy compounds, glycidyl ether epoxy compounds, Halogenated epoxy compounds such as glycidyl ester type epoxy compounds and brominated epoxy compounds, rubber modified epoxy compounds, urethane modified epoxy compounds, epoxy group-containing polyesters Le compounds, epoxy group-containing polyurethane compound, an epoxy group-containing acrylic compounds.
　また紫外線硬化性樹脂組成物は、芳香族ベンゼン環含有エポキシ化合物を上記単官能エポキシ化合物の一部として含有することが可能である。この場合、フェニルグリシジルエーテル、ベンジルグリシジルエーテル、４－ｔｅｒｔ－ブチルフェニルグリシジルエーテル、グリシジル２－メトキシフェニルエーテル等が挙げられる。 Further, the ultraviolet curable resin composition can contain an aromatic benzene ring-containing epoxy compound as a part of the monofunctional epoxy compound. In this case, phenyl glycidyl ether, benzyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, glycidyl 2-methoxyphenyl ether and the like can be mentioned.
　なお、単官能エポキシ化合物としては、上記長鎖炭化水素骨格を有する単官能エポキシ化合物と上記芳香族ベンゼン環含有エポキシ化合物のどちらにも該当しないものを含有することが可能である。このような単官能エポキシ化合物としては、例えば、ブチルグリシジルエーテル、ｔｅｒｔ－ブチルグリシジルエーテル、３－グリシジルオキシプロピル（ジメトキシ）メチルシラン、アリルグリシジルエーテル等が挙げられる。 In addition, as a monofunctional epoxy compound, it is possible to contain what does not correspond to any of the monofunctional epoxy compound which has the said long-chain hydrocarbon skeleton, and the said aromatic benzene ring containing epoxy compound. Examples of such monofunctional epoxy compounds include butyl glycidyl ether, tert-butyl glycidyl ether, 3-glycidyloxypropyl (dimethoxy) methylsilane, and allyl glycidyl ether.
　上記のような芳香族ベンゼン環含有エポキシ化合物は、単独で用いられてもよく、２種以上が併用されてもよい。 The above aromatic benzene ring-containing epoxy compounds may be used alone or in combination of two or more.
　（多官能オキセタン化合物）
　紫外線硬化性樹脂組成物は、多官能オキセタン化合物を含有している。多官能オキセタン化合物は、紫外線硬化性樹脂組成物の硬化反応を促進する働きを有するため、遅延硬化性を有しつつ、適度な硬化反応性を確保したい場合等に、紫外線硬化性樹脂組成物の硬化性を調整できると考えられる。すなわち、多官能オキセタン化合物は紫外線硬化性樹脂組成物の硬化急峻性を向上させる硬化促進剤である。硬化急峻性とは、紫外線硬化性樹脂組成物の硬化速度（単位時間あたりの粘度上昇）が短時間で急激に上昇して、硬化完了までの時間が速くなる性質のことを言う。多官能オキセタン化合物は、１分子中に２個以上のオキセタン基（環）を有するものであれば特に限定なく用いることができる。このような多官能オキセタン化合物は、３－エチル－３－ヒドロキシメチルオキセタン、２－エチルヘキシルオキセタン、キシリレンビスオキセタン、３－エチル－３｛［（３－エチルオキセタン－３－イル）メトキシ］メチル｝オキセタンなどである。オキセタン化合物は上記の中から１種単独で使用可能であり、あるいは２種以上を併用可能である。多官能オキセタン化合物は市販のものを使用することができ、例えば、東亜合成社のオキセタンシリーズ「ＯＸＴ１２１」、「ＯＸＴ２２１」等が挙げられる。その他には、オキセタン変性シリコーン等を使用することもできる。なかでも、粘度調整のしやすさ・揮発しにくさのバランス取りのしやすいものを用いることが好ましい。 (Polyfunctional oxetane compound)
The ultraviolet curable resin composition contains a polyfunctional oxetane compound. The polyfunctional oxetane compound has a function of accelerating the curing reaction of the ultraviolet curable resin composition. Therefore, when it is desired to ensure appropriate curing reactivity while having delayed curing properties, It is considered that the curability can be adjusted. That is, the polyfunctional oxetane compound is a curing accelerator that improves the steepness of curing of the ultraviolet curable resin composition. Curing steepness refers to the property that the curing rate (increased viscosity per unit time) of the ultraviolet curable resin composition rapidly increases in a short time, and the time until completion of curing is increased. The polyfunctional oxetane compound can be used without particular limitation as long as it has two or more oxetane groups (rings) in one molecule. Such polyfunctional oxetane compounds include 3-ethyl-3-hydroxymethyl oxetane, 2-ethylhexyl oxetane, xylylene bisoxetane, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} Such as oxetane. One oxetane compound can be used alone from the above, or two or more oxetane compounds can be used in combination. As the polyfunctional oxetane compound, a commercially available product can be used, and examples thereof include Oxetane series “OXT121” and “OXT221” manufactured by Toa Gosei Co., Ltd. In addition, oxetane-modified silicone can also be used. Among these, it is preferable to use a material that is easy to balance the ease of viscosity adjustment and the difficulty of volatilization.
　（その他の成分）
　本実施形態に係る紫外線硬化性樹脂組成物は、光重合開始剤を含有していてもよい。本実施形態において使用可能な光重合開始剤としては、光照射によって紫外線硬化性樹脂組成物のエポキシ基（及び、場合によっては、オキセタン基）を開環自重合させるための開始剤であれば特に限定はされない。光重合開始剤は、例えばイオン性光酸発生型であってもよく、非イオン性光酸発生剤であってもよい。 (Other ingredients)
The ultraviolet curable resin composition according to this embodiment may contain a photopolymerization initiator. The photopolymerization initiator that can be used in the present embodiment is particularly an initiator for ring-opening self-polymerization of an epoxy group (and, in some cases, an oxetane group) of an ultraviolet curable resin composition by light irradiation. There is no limitation. The photopolymerization initiator may be, for example, an ionic photoacid generator or a nonionic photoacid generator.
　具体例としては、イオン性光酸発生型については、芳香族ジアゾニウム塩、芳香族ハロニウム塩、芳香族スルホニウム塩などのオニウム塩類、鉄―アレン錯体、チタノセン錯体、アリールシラノール-アルミニウム錯体などの有機金属錯体類が挙げられる。これらは市販のものを使用することもできる。イオン性光酸発生型の光カチオン重合開始剤としては、例えば、旭電化工業社製の商品名「アデカオプトマーＳＰ１５０」、「アデカオプトマーＳＰ１７０」等の「アデカオプトマー」シリーズ、サンアプロ製の商品名「ＣＰＩ－２１０Ｓ」、ゼネラルエレクトロニクス社製の商品名「ＵＶＥ－１０１４」、サートマー社製の商品名「ＣＤ－１０１２」等が挙げられる。これらのイオン性光酸発生型の光カチオン重合開始剤は、単独で用いられてもよく、２種以上が併用されてもよい。 Specific examples of the ionic photoacid generating type include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, and organic metals such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Complexes are mentioned. These can also use a commercially available thing. As an ionic photoacid generation type photocationic polymerization initiator, for example, “Adekaoptomer SP150”, “Adekaoptomer SP170” and the like made by Asahi Denka Kogyo Co., Ltd. Examples include the product name “CPI-210S”, the product name “UVE-1014” manufactured by General Electronics Co., and the product name “CD-1012” manufactured by Sartomer. These ionic photoacid-generating photocationic polymerization initiators may be used alone or in combination of two or more.
　また、非イオン性光酸発生型としては、上記非イオン性光酸発生型の光カチオン重合開始剤としては特に限定されない。非イオン性光酸発生型としては、例えば、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ－ヒドロキシイミドホスホナート等が挙げられる。これらの非イオン性光酸発生型の光カチオン重合開始剤は、単独で用いられてもよく、２種以上が併用されてもよい。 Further, the nonionic photoacid generation type is not particularly limited as the nonionic photoacid generation type photocationic polymerization initiator. Examples of the nonionic photoacid generating type include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimidophosphonate and the like. These nonionic photoacid-generating photocationic polymerization initiators may be used alone or in combination of two or more.
　紫外線硬化性樹脂組成物には、さらに必要に応じて、エラストマーが含有されている。エラストマーは、紫外線硬化性樹脂組成物の硬化物（固定層３２）の物理的特性及び化学的特性を変化させる。すなわち、エラストマーを含有する紫外線硬化性樹脂組成物の硬化物は、エラストマーを含有していない紫外線硬化性樹脂組成物の硬化物に比べて、強度の向上、弾性率の低下、伸び率の向上といった物理的特性の変化が生じる。また、エラストマーを含有する紫外線硬化性樹脂組成物の硬化物は、エラストマーを含有していない紫外線硬化性樹脂組成物の硬化物に比べて、エラストマー中の極性基が被着体（例えば、第１板３０と第２板３１）との化学的相互作用を強めたり、エラストマー中のカチオン重合性置換基が被着体との化学結合を形成するといった化学的物特性の変化が生じる。このような化学的特性の変化が生じると、紫外線硬化性樹脂組成物の硬化物と被着体との密着性（接着強度）が向上する場合がある。 The ultraviolet curable resin composition further contains an elastomer as necessary. The elastomer changes the physical properties and chemical properties of the cured product (fixed layer 32) of the ultraviolet curable resin composition. That is, the cured product of the ultraviolet curable resin composition containing an elastomer has an improved strength, a reduced elastic modulus, and an improved elongation rate compared to a cured product of an ultraviolet curable resin composition that does not contain an elastomer. Changes in physical properties occur. In addition, the cured product of the ultraviolet curable resin composition containing the elastomer has a polar group in the elastomer that adheres to the adherend (for example, the first material, for example, as compared with the cured product of the ultraviolet curable resin composition that does not contain the elastomer. Changes in chemical properties such as strengthening the chemical interaction between the plate 30 and the second plate 31) or forming a chemical bond with the adherend by the cationically polymerizable substituent in the elastomer occur. When such a change in chemical characteristics occurs, the adhesion (adhesive strength) between the cured product of the ultraviolet curable resin composition and the adherend may be improved.
　エラストマーは、ポリオレフィン系、ポリスチレン系、ポリエステル系、ポリウレタン系、シリコーン系などの各種高分子物質で形成されている。また、これらのエラストマーは、カルボキシル基、水酸基、シアノ基、チオール基、アミノ基などの極性の大きな置換基で変性されていたりエポキシ基及びオキセタン基のようなカチオン重合性置換基で変性されていたりすると、より好ましい。変性されたエラストマーは、変性されていない場合よりも、上記物理的特性及び化学的特性が向上する可能性があるからである。エラストマーは１種単独で使用可能であり、あるいは２種以上を併用可能である。 The elastomer is formed of various polymer materials such as polyolefin, polystyrene, polyester, polyurethane, and silicone. In addition, these elastomers may be modified with a substituent having a large polarity such as a carboxyl group, a hydroxyl group, a cyano group, a thiol group, or an amino group, or may be modified with a cationic polymerizable substituent such as an epoxy group or an oxetane group. Then, it is more preferable. This is because the modified elastomer may have improved physical and chemical properties as compared to the case where it has not been modified. One type of elastomer can be used alone, or two or more types can be used in combination.
　紫外線硬化性樹脂組成物中におけるエラストマーの形態は特に限定されず、粒子であってもよいし、溶解した状態であってもよいし、あるいは粒子と溶解状態の両方の形態が併存していてもよい。またエラストマーとしては、無色なものを選ぶことで、紫外線硬化性樹脂組成物中に添加したエラストマーによる光学的影響を低減できる。またエラストマーとしては、紫外線硬化性樹脂組成物の硬化物と同程度の透光性を有するものを選ぶことで、紫外線硬化性樹脂組成物中に添加したエラストマーによる光学的影響を低減できる。無色とはエラストマーと、このエラストマーが添加される紫外線樹脂組成物との色差△Ｅ＊の値が３．２以下、更に１．６以下、更に０．８以下である。色差△Ｅ＊の値が３．２以下、更に１．６以下であれば、一般的な目視検査の再現性等からみても許容色差であり、実質的にエラストマーによる着色が無い考えられる。なお色差の測定方法及び評価方法はＪＩＳ　Ｌ　０８４０及びＪＩＳ　Ｌ　０８０５を参照すれば良い。またエラストマーによる光散乱性を小さくすることで硬化物の透明性を高められる。すなわちエラストマーが含有された紫外線硬化性樹脂組成物の硬化物において、ヘイズ値が１０％以下、更に８％以下、５％以下であればエラストマーによる透明性への影響は少ない。すなわち実質的にエラストマーは透明（すなわち白濁性が少ない）であるとして良い。ヘイズ値の測定は市販のヘイズメータを使って、ＪＩＳ－Ｋ－７１３６等に準じて行なえば良い。ヘイズ値は、ヘイズ（％）＝拡散透過率／全光線透過率＊１００（％）の計算式で求められる。 The form of the elastomer in the ultraviolet curable resin composition is not particularly limited, and may be a particle, a dissolved state, or a combination of both particles and a dissolved state. Good. Further, by selecting a colorless elastomer, it is possible to reduce the optical influence of the elastomer added to the ultraviolet curable resin composition. Moreover, the optical influence by the elastomer added in the ultraviolet curable resin composition can be reduced by selecting what has a translucency comparable as the hardened | cured material of an ultraviolet curable resin composition as an elastomer. Colorless means that the value of the color difference ΔE * between the elastomer and the ultraviolet resin composition to which the elastomer is added is 3.2 or less, further 1.6 or less, and further 0.8 or less. If the value of the color difference ΔE * is 3.2 or less, and further 1.6 or less, it is an allowable color difference from the viewpoint of reproducibility of general visual inspection and the like, and it is considered that there is substantially no coloring due to the elastomer. Note that JIS L 0840 and JIS L 0805 may be referred to for the color difference measurement method and evaluation method. Further, the transparency of the cured product can be increased by reducing the light scattering property of the elastomer. That is, in the cured product of the ultraviolet curable resin composition containing the elastomer, the elastomer has little effect on the transparency if the haze value is 10% or less, further 8% or less, and 5% or less. That is, the elastomer may be substantially transparent (that is, less turbid). The haze value may be measured according to JIS-K-7136 using a commercially available haze meter. The haze value is obtained by a calculation formula of haze (%) = diffuse transmittance / total light transmittance * 100 (%).
　紫外線硬化性樹脂組成物には、さらに必要に応じて、通常用いられる各種添加剤を添加してもよい。このような添加剤の具体例としては、例えば、シランカップリング剤；酸化アルミニウム、酸化珪素、炭酸カルシウム、酸化マグネシウムなどの無機質充填剤；過酸化物及びアゾ化合物などの重合促進剤；消泡剤；陽イオン性、陰イオン性、非イオン性、両性の各種界面活性剤；チクソトロピー剤；カップリング剤；アンチモン類及びブロム化合物などの難燃材；無機顔料、有機顔料、染料などの着色剤等が挙げられる。 The ultraviolet curable resin composition may further contain various commonly used additives as necessary. Specific examples of such additives include, for example, silane coupling agents; inorganic fillers such as aluminum oxide, silicon oxide, calcium carbonate, and magnesium oxide; polymerization accelerators such as peroxides and azo compounds; Cationic, anionic, nonionic and amphoteric surfactants; thixotropic agents; coupling agents; flame retardants such as antimony and bromo compounds; colorants such as inorganic pigments, organic pigments and dyes Is mentioned.
　（紫外線硬化性樹脂組成物の調製）
　紫外線硬化性樹脂組成物を製造する方法は、特に限定されず、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリウムミキサー、ニーダー、３本ロール等の混合機を用いて、上述したような配合成分を混合する方法が挙げられる。なお、紫外線硬化性樹脂組成物は、上述した必須成分および必要に応じて添加される任意成分が、使用時点で均一に混合されておればよく、流通時及び貯蔵時などに全量が混合されている必要はない。即ち、流通時及び貯蔵時などの状況によっては、２種以上に分割しておき、使用直前に配合して用いてもよい。紫外線硬化性樹脂組成物は、必要成分を全て混合した直後において、液状状態であることが好ましい。 (Preparation of UV curable resin composition)
The method for producing the ultraviolet curable resin composition is not particularly limited. For example, the blending components as described above using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, and a three roll. The method of mixing is mentioned. In addition, the ultraviolet curable resin composition should just mix the essential component mentioned above and the arbitrary component added as needed uniformly at the time of use, and the whole quantity is mixed at the time of distribution, storage, etc. There is no need to be. That is, depending on the situation such as distribution and storage, it may be divided into two or more types and blended immediately before use. The ultraviolet curable resin composition is preferably in a liquid state immediately after mixing all necessary components.
　紫外線硬化性樹脂組成物は、多官能エポキシ化合物と単官能エポキシ化合物と多官能オキセタン化合物との合計量１００質量部に対して、多官能エポキシ化合物及び多官能オキセタン化合物を合計で３０質量部以上９５質量部以下含有し、単官能エポキシ化合物を７０質量部以下５質量部以上含有している。 The ultraviolet curable resin composition has a total of 30 parts by mass or more of the polyfunctional epoxy compound and the polyfunctional oxetane compound with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. It is contained in an amount of up to 70 parts by mass and contains up to 5 parts by mass of a monofunctional epoxy compound.
　ここで、紫外線硬化性樹脂組成物は、多官能エポキシ化合物と単官能エポキシ化合物と多官能オキセタン化合物との合計量１００質量部に対して、多官能オキセタン化合物を１質量部以上３０質量部以下、より好ましくは３質量部以上１０質量部以下となるように配合するのが好ましい。多官能オキセタン化合物を１質量部以上３０質量部以下の範囲で配合することにより、紫外線硬化性樹脂組成物の硬化反応速度を適度に調整することが可能となる。多官能オキセタン化合物の含有量が上記範囲の場合、紫外線硬化性樹脂組成物は、多官能エポキシ化合物と単官能エポキシ化合物と多官能オキセタン化合物との合計量１００質量部に対して、多官能エポキシ化合物を０質量部以上９４質量部以下含有し、好ましくは、２０質量部以上９２質量部以下含有することになる。 Here, the ultraviolet curable resin composition is 1 part by mass or more and 30 parts by mass or less of the polyfunctional oxetane compound with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. More preferably, it is blended so as to be 3 parts by mass or more and 10 parts by mass or less. By mix | blending a polyfunctional oxetane compound in 1 mass part or more and 30 mass parts or less, it becomes possible to adjust moderately the cure reaction rate of an ultraviolet curable resin composition. When the content of the polyfunctional oxetane compound is in the above range, the ultraviolet curable resin composition is a polyfunctional epoxy compound with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. 0 parts by mass or more and 94 parts by mass or less, preferably 20 parts by mass or more and 92 parts by mass or less.
　また単官能エポキシ化合物はその全部が長鎖炭化水素骨格を有する単官能エポキシ化合物であってもよく、この場合、紫外線硬化性樹脂組成物は、多官能エポキシ化合物と単官能エポキシ化合物と多官能オキセタン化合物との合計量１００質量部に対して、長鎖炭化水素骨格を有する単官能エポキシ化合物を７０質量部以下５質量部以上含有している。好ましくは、紫外線硬化性樹脂組成物は、多官能エポキシ化合物と単官能エポキシ化合物と多官能オキセタン化合物との合計量１００質量部に対して、長鎖炭化水素骨格を有する単官能エポキシ化合物を６５質量部以下１０質量部以上含有している。長鎖単官能エポキシ化合物の配合量が７０質量部以下５質量部以上の範囲であれば、十分な遅延硬性が得られ、かつ一定の時間が経過した後に紫外線硬化性樹脂組成物が硬化しやすくなる。 Further, the monofunctional epoxy compound may be a monofunctional epoxy compound having a long-chain hydrocarbon skeleton, and in this case, the ultraviolet curable resin composition is composed of a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane. The monofunctional epoxy compound having a long-chain hydrocarbon skeleton is contained in an amount of 70 parts by mass or less and 5 parts by mass or more with respect to 100 parts by mass in total with the compound. Preferably, the ultraviolet curable resin composition has 65 masses of the monofunctional epoxy compound having a long-chain hydrocarbon skeleton with respect to 100 mass parts of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. 10 parts by mass or less. If the amount of the long-chain monofunctional epoxy compound is in the range of 70 parts by mass or less and 5 parts by mass or more, sufficient delayed hardness is obtained, and the UV curable resin composition is easily cured after a certain period of time. Become.
　また紫外線硬化性樹脂組成物は、多官能エポキシ化合物と単官能エポキシ化合物と多官能オキセタン化合物との合計量１００質量部に対して、芳香族ベンゼン環含有エポキシ化合物を１質量部以上４０質量部以下含有している。ここで、芳香族ベンゼン環含有エポキシ化合物の含有量は、多官能エポキシ化合物として配合されている芳香族ベンゼン環含有エポキシ化合物と単官能エポキシ化合物として配合されている芳香族ベンゼン環含有エポキシ化合物との合計量である。 In addition, the ultraviolet curable resin composition has an aromatic benzene ring-containing epoxy compound in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. Contains. Here, the content of the aromatic benzene ring-containing epoxy compound is the ratio between the aromatic benzene ring-containing epoxy compound formulated as a polyfunctional epoxy compound and the aromatic benzene ring-containing epoxy compound formulated as a monofunctional epoxy compound. Total amount.
　また紫外線硬化性樹脂組成物中の光重合開始剤の含有量は、特に限定されないが、通常、多官能エポキシ化合物と単官能エポキシ化合物と多官能オキセタン化合物との合計量１００質量部に対して、０．１質量部以上１０質量部以下である。光重合開始剤の含有量が０．１質量部以上であれば、多官能エポキシ化合物と単官能エポキシ化合物と多官能オキセタン化合物の重合が十分に行われ、遅延時間が極端に長くなることもない。上記開始剤の含有量が１０質量部以下であれば、紫外線硬化性樹脂組成物の硬化反応が速くなりすぎることがなく、作業性（遅延硬化性など）が失われたり、深部硬化性が悪化したりする（不均一な硬化物となる）こともない。 Further, the content of the photopolymerization initiator in the ultraviolet curable resin composition is not particularly limited, but is usually 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. It is 0.1 mass part or more and 10 mass parts or less. When the content of the photopolymerization initiator is 0.1 parts by mass or more, the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound are sufficiently polymerized, and the delay time does not become extremely long. . If the content of the initiator is 10 parts by mass or less, the curing reaction of the UV curable resin composition will not be too fast, and workability (such as delayed curing) will be lost, or the deep curability will deteriorate. It does not occur (becomes a non-uniform cured product).
　また紫外線硬化性樹脂組成物がエラストマーを含有する場合、その含有量は、特に限定されないが、多官能エポキシ化合物と単官能エポキシ化合物と多官能オキセタン化合物との合計量１００質量部に対して、０．１質量部以上１００質量部以下の範囲であることが好ましい。エラストマーの含有量が、この範囲であれば、紫外線硬化性樹脂組成物の硬化物（固定層３２）の上記物理的特性、化学的特性などの特性を変化させやすくなる。すなわち、エラストマーの含有量が上記の範囲から逸脱すると、紫外線硬化性樹脂組成物の硬化物の上記物理的特性及び化学的特性を変化させにくくなる。 Moreover, when an ultraviolet curable resin composition contains an elastomer, the content is not particularly limited, but is 0 with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. It is preferably in the range of 1 to 100 parts by mass. When the content of the elastomer is within this range, it becomes easy to change the physical properties and chemical properties of the cured product (fixed layer 32) of the ultraviolet curable resin composition. That is, when the content of the elastomer deviates from the above range, it is difficult to change the physical characteristics and chemical characteristics of the cured product of the ultraviolet curable resin composition.
　このような紫外線硬化性樹脂組成物は、ＬＥＤ方式の紫外線硬化装置等で紫外光（ＵＶ）を照射して露光して硬化させることにより、熱線による熱歪の悪影響を抑制して硬化される。さらに、紫外線硬化性樹脂組成物は遅延硬化性を有するので、ＵＶ照射後、一定の期間、低粘度状態を維持し、その後速やかに粘度上昇して硬化する。従って、ＵＶ照射した後に、電子部品等の被着体と合わせることが可能なので、ＵＶによって電子部品等が劣化することもない。また、金属、ガラス、プラスチックなど、様々の種類の基材に対して優れた接着性を発揮する。さらに、紫外線硬化性樹脂組成物は従来のような遅延硬化剤を含有していないため、透明性及び物性にも優れている。そのため、小型化、高精密化、透明性が要求される各種光学部品の接着剤、有機ＥＬ素子用封止材などの用途として適している。 Such an ultraviolet curable resin composition is cured while being irradiated with ultraviolet light (UV) by an LED type ultraviolet curing device or the like to be exposed and cured, thereby suppressing the adverse effect of heat distortion caused by heat rays. Furthermore, since the ultraviolet curable resin composition has delayed curing properties, it maintains a low viscosity state for a certain period after UV irradiation, and then rapidly increases in viscosity and cures. Therefore, since it can be combined with an adherend such as an electronic component after UV irradiation, the electronic component is not deteriorated by UV. In addition, it exhibits excellent adhesion to various types of substrates such as metal, glass and plastic. Furthermore, since the ultraviolet curable resin composition does not contain a conventional delayed curing agent, it is excellent in transparency and physical properties. Therefore, it is suitable for applications such as adhesives for various optical components that require miniaturization, high precision, and transparency, and sealing materials for organic EL elements.
　有機ＥＬ素子用封止材として用いる場合には、温度・湿度が変化する環境においても密着力・透明性を維持できる。特にトップエミッション型の有機ＥＬディスプレイ等では、発光面の樹脂の透明性が重要となるため、本実施形態の紫外線硬化性樹脂組成物を用いることが非常に好ましい。さらに、有機ＥＬ素子などは紫外線でダメージを受けやすいので、基板の貼り合せ工程において、有機ＥＬ素子がついていない側の基板に紫外線硬化性樹脂組成物を塗布し、ＵＶ照射をしてから素子側基板と貼り合せ・アライメント（この時は低粘度のため調整可）する。このことにより、ＵＶ・熱によるダメージをさけることが可能となる。この点、本実施の形態に係る紫外線硬化性樹脂組成物は、アライメントのために必要十分な遅延時間を提供することができる。また、接着させてからのＵＶ照射では、カラーフィルター越しでの照射となるため、暗部が形成されてしまい、未硬化部分が発生するおそれがあるが、こういった問題も本実施の形態の紫外線硬化性樹脂組成物では生じにくい。 When used as a sealing material for organic EL elements, adhesion and transparency can be maintained even in an environment where temperature and humidity change. Particularly in a top emission type organic EL display or the like, since the transparency of the resin on the light emitting surface is important, it is very preferable to use the ultraviolet curable resin composition of the present embodiment. Furthermore, since organic EL elements and the like are easily damaged by ultraviolet rays, in the substrate bonding step, an ultraviolet curable resin composition is applied to the substrate on which the organic EL elements are not attached, and the element side is subjected to UV irradiation. Bond and align with the substrate (adjustable due to low viscosity at this time). This makes it possible to avoid damage caused by UV and heat. In this regard, the ultraviolet curable resin composition according to the present embodiment can provide a necessary and sufficient delay time for alignment. In addition, since UV irradiation after bonding is performed through the color filter, a dark part may be formed and an uncured part may be generated. It is difficult to occur with a curable resin composition.
　上記紫外線硬化性樹脂組成物は、活性エネルギー線の照射直後は液状を保ち、一定時間経過後に硬化する遅延硬化性を示すものである。このような紫外線硬化性樹脂組成物が接着剤であれば、遅延硬化型の接着剤が得られる。ここで言う遅延硬化型接着剤とは、硬化反応を開始させるに必要なエネルギーを付与したのち一定時間は液状を保つことで部材同士を貼り合せる時間的な猶予を持つ接着剤（すなわち、可使時間の長い接着剤）のことをいう。しかも、遅延硬化型接着剤とは、貼り合せ後に光又は熱といったエネルギーを追加で付与せずとも硬化反応が充分に進行し、硬化が完了する接着剤のことを言う。また、遅延硬化型接着剤は活性エネルギー線を照射されることで初めて活性化され、硬化反応が開始される。そのため、活性エネルギー線を照射されなければ硬化することはほとんどなく、溶剤型接着剤及びシアノアクリレート系瞬間接着剤のように、通常環境下で自発的に硬化する接着剤とは異なる。 The ultraviolet curable resin composition is in a liquid state immediately after irradiation with active energy rays and exhibits delayed curability that cures after a certain period of time. If such an ultraviolet curable resin composition is an adhesive, a delayed curable adhesive can be obtained. The delayed-curing type adhesive here refers to an adhesive having a time allowance for bonding the members together by maintaining the liquid state for a certain period of time after applying the energy necessary to start the curing reaction (ie, usable adhesive). A long-time adhesive). In addition, the delayed-curing adhesive refers to an adhesive that undergoes a curing reaction sufficiently to complete curing without additionally applying energy such as light or heat after bonding. The delayed-curing adhesive is activated only when irradiated with active energy rays, and a curing reaction is started. Therefore, it hardly cures if it is not irradiated with active energy rays, and is different from an adhesive that spontaneously cures in a normal environment, such as a solvent-type adhesive and a cyanoacrylate instantaneous adhesive.
　上記紫外線硬化性樹脂組成物において、遅延時間については、紫外線硬化性樹脂組成物の組成及び活性エネルギー線の照射強度、ならびに紫外線硬化性樹脂組成物の温度などによって変化する。紫外線硬化性樹脂組成物を接着剤に用いて実際の貼り合せ工程を想定すると、温度２５℃における雰囲気下で、５０ｍＪ／ｃｍ２以上の照射量で波長３６５ｎｍの活性エネルギー線が照射された後、５秒間以上６０分間以内は液状であり、その後、１２時間以内に硬化することが好ましい。このような性状となるように、紫外線硬化性樹脂組成物の組成などを調整することが好ましい。なお、「遅延時間」とは、紫外線硬化性樹脂組成物が活性エネルギー線を照射された後から液状を保つ間の時間をいう。この場合、「液状」とは紫外線硬化性樹脂組成物の粘度が５００００Ｐａ・ｓ以下の状態である。また「硬化」とは紫外線硬化性樹脂組成物の粘度が５００００Ｐａ・ｓよりも大きくなった状態である。遅延時間が長いと紫外線硬化性樹脂組成物の塗布又は紫外線硬化性樹脂組成物による部材の接着などが可能となり、紫外線硬化性樹脂組成物の可使時間が長くて取り扱い性に優れるといえる。 In the ultraviolet curable resin composition, the delay time varies depending on the composition of the ultraviolet curable resin composition, the irradiation intensity of active energy rays, the temperature of the ultraviolet curable resin composition, and the like. Assuming an actual bonding process using an ultraviolet curable resin composition as an adhesive, after an active energy ray having a wavelength of 365 nm is irradiated with an irradiation dose of 50 mJ / cm 2 or more in an atmosphere at a temperature of 25 ° C., It is preferably liquid for 5 seconds to 60 minutes and then cured within 12 hours. It is preferable to adjust the composition of the ultraviolet curable resin composition and the like so as to achieve such properties. The “delay time” refers to the time during which the ultraviolet curable resin composition is kept in a liquid state after being irradiated with active energy rays. In this case, “liquid” means a state in which the viscosity of the ultraviolet curable resin composition is 50000 Pa · s or less. “Curing” is a state in which the viscosity of the ultraviolet curable resin composition is greater than 50000 Pa · s. When the delay time is long, application of the ultraviolet curable resin composition or adhesion of members by the ultraviolet curable resin composition becomes possible, and it can be said that the usable time of the ultraviolet curable resin composition is long and the handling property is excellent.
　（積層体の製造）
　上記積層体３００は上記紫外線硬化性樹脂組成物を接着剤として用いて製造される。積層体３００を製造するにあたっては、接着剤配置工程と照射工程と位置合わせ工程と貼り合わせ工程と養生工程とを順次行う。 (Manufacture of laminates)
The laminate 300 is manufactured using the ultraviolet curable resin composition as an adhesive. In manufacturing the laminated body 300, an adhesive placement process, an irradiation process, an alignment process, a bonding process, and a curing process are sequentially performed.
　図２Ａのように、接着剤配置工程では、第１板３０の片面に接着剤（未硬化の紫外線硬化性樹脂組成物）３２１を配置する。接着剤３２１を配置する方法は、塗布及び印刷などの任意の方法が採用される。接着剤３２１は、例えば、３０ｇ／ｍ２以上１５００ｇ／ｍ２以下の量で配置される。また接着剤３２１は、第１板３０の全面に均等に配置してもよいし、線状又は格子状等に配置してもよい。接着剤３２１は、硬化後の固定層３２と同程度の透明性を有していても良いし、半透明又は不透明であっても良い。 As shown in FIG. 2A, in the adhesive placement step, an adhesive (uncured ultraviolet curable resin composition) 321 is placed on one side of the first plate 30. Arbitrary methods, such as application | coating and printing, are employ | adopted for the method of arrange | positioning the adhesive agent 321. FIG. For example, the adhesive 321 is disposed in an amount of 30 g / m 2 or more and 1500 g / m 2 or less. Further, the adhesive 321 may be evenly arranged on the entire surface of the first plate 30, or may be arranged in a linear shape or a lattice shape. The adhesive 321 may have the same degree of transparency as the fixed layer 32 after curing, or may be translucent or opaque.
　図２Ｂのように、照射工程では、接着剤配置工程後に、第１板３０に配置した未硬化の接着剤３２１に紫外線を含む活性エネルギー線４０を照射する。活性エネルギー線４０は紫外線以外に可視光等を含んでいてもよい。この活性エネルギー線４０の照射により接着剤３２１の光カチオン重合による硬化が開始される。また、この照射工程により、接着剤３２１が固定層３２にまで硬化するのに必要な量の活性エネルギー線４０が照射される。活性エネルギー線４０の照射は、例えば、紫外線ランプなどの照明装置４１が用いられる。活性エネルギー線４０の照射量は、例えば、５０ｍＪ／ｃｍ２以上３０００ｍＪ／ｃｍ２以下とすることができる。 As shown in FIG. 2B, in the irradiation step, the active energy ray 40 including ultraviolet rays is irradiated to the uncured adhesive 321 disposed on the first plate 30 after the adhesive placement step. The active energy ray 40 may contain visible light or the like in addition to ultraviolet rays. By the irradiation of the active energy ray 40, the adhesive 321 is cured by photocationic polymerization. In addition, the irradiation step irradiates the active energy ray 40 in an amount necessary for the adhesive 321 to cure to the fixed layer 32. For example, an illumination device 41 such as an ultraviolet lamp is used for irradiation with the active energy ray 40. The dose of the active energy ray 40, for example, be a 50 mJ / cm 2 or more 3000 mJ / cm 2 or less.
　位置合わせ工程では、照射工程後に、第１板３０と第２板３１とを所定の位置に配置する。例えば、第２板３１の上方に第１板３０を配置し、所定の貼り合わせ位置となるように第１板３０と第２板３１とを互い位置合わせする。この場合、第１板３０の接着剤３２１を配置した面が第２板３１の片面と対向するようにする。 In the alignment step, the first plate 30 and the second plate 31 are arranged at predetermined positions after the irradiation step. For example, the 1st board 30 is arrange | positioned above the 2nd board 31, and the 1st board 30 and the 2nd board 31 are mutually aligned so that it may become a predetermined bonding position. In this case, the surface of the first plate 30 on which the adhesive 321 is disposed is made to face one surface of the second plate 31.
　図２Ｄのように、貼り合わせ工程は、位置合わせ工程後、未硬化の接着剤３２１を介して第１板３０と第２板３１とを重ねて貼り合わせる。このとき、接着剤３２１が線状に塗布されている場合は、貼り合わせ時の圧力により、第１板３０と第２板３１の間に接着剤３２１がほぼ均等な厚みとなるように広がる。 As shown in FIG. 2D, in the bonding step, the first plate 30 and the second plate 31 are stacked and bonded via an uncured adhesive 321 after the positioning step. At this time, when the adhesive 321 is applied linearly, the adhesive 321 spreads between the first plate 30 and the second plate 31 so as to have a substantially uniform thickness due to the pressure at the time of bonding.
　図２Ｅのように、養生工程では、貼り合わせ工程後、未硬化の接着剤３２１を硬化させて固定層３２を形成し、この固定層３２で第１板３０と第２板３１とを接着する。養生工程における接着剤３２１の硬化は、照射工程により照射された活性エネルギー線４０により行われる。従って、養生工程では、活性エネルギー線４０を照射する必要はほとんどない。また、第１板３０と第２板３１とが紫外線を透過しない場合でも、接着剤３２１の硬化が進む。従って、養生工程後に、紫外線の照射不足による未硬化の部分が固定層３２に生じにくくなり、固定層３２による層間（第１板３０と第２板３１の間）の密着強度を高くすることができる。また未硬化の部分が固定層３２に生じにくいため、第１板３０と第２板３１の間から未硬化の接着剤３２１が染み出てくることも少なくなり、積層体３００の周囲を汚染しにくくなる。 As shown in FIG. 2E, in the curing process, after the bonding process, the uncured adhesive 321 is cured to form the fixed layer 32, and the first plate 30 and the second plate 31 are bonded by the fixed layer 32. . Curing of the adhesive 321 in the curing process is performed by the active energy rays 40 irradiated in the irradiation process. Therefore, there is almost no need to irradiate the active energy ray 40 in the curing process. Even when the first plate 30 and the second plate 31 do not transmit ultraviolet rays, the curing of the adhesive 321 proceeds. Therefore, after the curing process, an uncured portion due to insufficient ultraviolet irradiation is less likely to occur in the fixed layer 32, and the adhesion strength between the fixed layers 32 (between the first plate 30 and the second plate 31) can be increased. it can. In addition, since an uncured portion hardly occurs in the fixed layer 32, the uncured adhesive 321 is less likely to ooze out between the first plate 30 and the second plate 31 and contaminates the periphery of the laminate 300. It becomes difficult.
　また上記のような積層体３００の製造方法で使用される接着剤３２１は、活性エネルギー線４０により硬化が開始され、接着剤配置工程から貼り合わせ工程直後まで液状乃至半硬化状態であり、養生工程で完全に硬化し、硬化後には透明性を有する遅延硬化型接着剤である。従って、積層体３００の製造方法では、貼り合わせ工程の終了直前までにおいて、接着剤（未硬化の紫外線硬化性樹脂組成物）３２１は、第１板３０と第２板３１とをリワーク可能に貼り合わせている。ここで、「リワーク」とは、紫外線硬化性樹脂を介在させて第１板と第２板とを貼りあわせた後、第１板と第２板とを剥がして各々を再利用することを意味する。また「リワーク」とは、紫外線硬化性樹脂を介在させて第１板と第２板とを貼りあわせた後、第１板と第２板の互いの位置をずらして調整（アライメント）することを意味する。ここで、リワーク可能な紫外線硬化性樹脂は完全硬化する前（固定層になる前）の状態である。 In addition, the adhesive 321 used in the method for manufacturing the laminate 300 as described above is cured by the active energy ray 40 and is in a liquid or semi-cured state from the adhesive placement step to immediately after the bonding step. This is a delayed-curing type adhesive that is completely cured at the end and has transparency after curing. Therefore, in the manufacturing method of the laminated body 300, the adhesive (uncured ultraviolet curable resin composition) 321 is bonded to the first plate 30 and the second plate 31 so that they can be reworked until just before the end of the bonding step. It is matched. Here, “rework” means that the first plate and the second plate are bonded together with an ultraviolet curable resin interposed therebetween, and then the first plate and the second plate are peeled off and reused. To do. “Rework” refers to adjusting the alignment of the first plate and the second plate by shifting the positions of the first plate and the second plate after the UV curable resin is interposed therebetween. means. Here, the reworkable UV curable resin is in a state before being completely cured (before becoming a fixed layer).
　以下、本発明を実施例によって具体的に説明する。 Hereinafter, the present invention will be specifically described by way of examples.
　［紫外線硬化性樹脂組成物の調製］
　プライミクス社製のホモディスパーを使用し、下記表１に示す配合組成（質量部）で各成分を均一に混合し（２５００ｒｐｍ、１０分）、実施例１～４および比較例１～４に示す紫外線硬化性樹脂組成物を調製した。なお、表１で用いた各成分の詳細は下記の通りである。
（Ａ）多官能エポキシ化合物
（Ａ１）２官能ポリブタジエンエポキシ樹脂（「Ｒ－４５ＥＰＴ」、ナガセケムテックス株式会社製、芳香族ベンゼン環含有エポキシ化合物に該当しない）
（Ａ２）ビスフェノールＡ型２官能エポキシ樹脂（「ＹＤ－８１２５」、新日鐵化学製、芳香族ベンゼン環含有エポキシ化合物に該当する）
（Ｂ）単官能エポキシ化合物
（Ｂ１）炭素数１１～１５の単官能エポキシ樹脂の混合物（リカレジンＬ－２００、新日本理化社製、芳香族ベンゼン環含有エポキシ化合物に該当しない）
（Ｂ２）芳香族ベンゼン環含有の単官能エポキシ化合物（デナコールＥＸ－１４１、ナガセケムテクス社製）
（Ｂ３）長鎖炭化水素骨格を有する単官能エポキシ化合物でなく、且つ芳香族ベンゼン環含有エポキシ化合物でない単官能エポキシ化合物（デナコールＥＸ－１１１、ナガセケムテックス社製）
（Ｃ）多官能オキセタン化合物
２官能オキセタン樹脂（「ＯＸＴ２２１」、東亜合成化学工業（株）社製）
（Ｄ）光重合開始剤
光カチオン重合開始剤（「ＳＰ－１７０」、旭電化工業社製）
（Ｅ）エラストマー
カルボキシル基含有ニトリルブタジエンゴム（「ＸＥＲ３２Ｃ」、ＪＳＲ株式会社製）
　［積層体の製造］
　積層体としてスマートフォンの表示装置を製造した。積層体は第１板として透明板を使用し、第２板として表示板を使用した。第１板はポリカーボネート製の透明板であって、長辺の長さが１４０ｍｍ、短辺の長さが８０ｍｍ、厚みが１ｍｍであった。また第１板は紫外線を透過せず、全光透過率が９５％であった。第２板は液晶パネルであって、長辺の長さが１３０ｍｍ、短辺の長さが７５ｍｍ、厚みが０．４ｍｍであった。また第２板は紫外線を透過しないものであった。そして、第１板と第２板とを上記紫外線硬化性樹脂組成物の硬化物からなる固定層で接着して固定することにより、第１板と第２板とが平行に配置された積層板を製造した。 [Preparation of UV curable resin composition]
Using a homodisper manufactured by Primix, each component was uniformly mixed (2500 rpm, 10 minutes) with the composition (parts by mass) shown in Table 1 below, and ultraviolet rays shown in Examples 1 to 4 and Comparative Examples 1 to 4 A curable resin composition was prepared. The details of each component used in Table 1 are as follows.
(A) Multifunctional epoxy compound (A1) Bifunctional polybutadiene epoxy resin ("R-45EPT", manufactured by Nagase ChemteX Corporation, does not fall under the aromatic benzene ring-containing epoxy compound)
(A2) Bisphenol A type bifunctional epoxy resin (“YD-8125”, manufactured by Nippon Steel Chemical Co., Ltd., applicable to aromatic benzene ring-containing epoxy compounds)
(B) Monofunctional epoxy compound (B1) Mixture of monofunctional epoxy resin having 11 to 15 carbon atoms (Licar Resin L-200, manufactured by Shin Nippon Rika Co., Ltd., does not correspond to an aromatic benzene ring-containing epoxy compound)
(B2) A monofunctional epoxy compound containing an aromatic benzene ring (Denacol EX-141, manufactured by Nagase ChemteX Corporation)
(B3) A monofunctional epoxy compound that is not a monofunctional epoxy compound having a long-chain hydrocarbon skeleton and is not an aromatic benzene ring-containing epoxy compound (Denacol EX-111, manufactured by Nagase ChemteX Corporation)
(C) Polyfunctional oxetane compound bifunctional oxetane resin ("OXT221", manufactured by Toa Gosei Chemical Co., Ltd.)
(D) Photopolymerization initiator Photocationic polymerization initiator (“SP-170”, manufactured by Asahi Denka Kogyo Co., Ltd.)
(E) Elastomer carboxyl group-containing nitrile butadiene rubber ("XER32C", manufactured by JSR Corporation)
[Manufacture of laminates]
A smartphone display device was manufactured as a laminate. The laminate used a transparent plate as the first plate and a display plate as the second plate. The first plate was a polycarbonate transparent plate having a long side length of 140 mm, a short side length of 80 mm, and a thickness of 1 mm. The first plate did not transmit ultraviolet light, and the total light transmittance was 95%. The second plate was a liquid crystal panel having a long side length of 130 mm, a short side length of 75 mm, and a thickness of 0.4 mm. The second plate did not transmit ultraviolet light. And the 1st board and the 2nd board are bonded and fixed with the fixed layer which consists of a hardened material of the above-mentioned ultraviolet curable resin composition, and the 1st board and the 2nd board are arranged in parallel Manufactured.
　積層板を製造するにあたっては、接着剤配置工程と照射工程と位置合わせ工程と貼り合わせ工程と養生工程とを順次行った。 In manufacturing the laminate, an adhesive placement process, an irradiation process, an alignment process, a bonding process, and a curing process were sequentially performed.
　接着剤配置工程では、未硬化の紫外線硬化性樹脂組成物を接着剤として第１板の片面に格子状に塗布した。接着剤の塗布量は１００ｇ／ｍ２とした。 In the adhesive placement step, an uncured ultraviolet curable resin composition was applied as an adhesive in a grid pattern on one side of the first plate. The amount of adhesive applied was 100 g / m 2 .
　照射工程では、第１板の片面に塗布された接着剤に紫外線を照射した。紫外線の光源としてはＵＶ－ＬＥＤ光源（浜松ホトニクス株式会社製、ＬＣ－Ｌ２、中心波長３６５ｎｍ）を使用し、紫外線を１００ｍＷ／ｃｍ２の照度で５秒間照射し、合計５００ｍＪ／ｃｍ２の照射量とした。 In the irradiation step, the adhesive applied to one side of the first plate was irradiated with ultraviolet rays. As a UV light source, a UV-LED light source (Hamamatsu Photonics Co., Ltd., LC-L2, center wavelength 365 nm) is used, and UV light is irradiated at an illuminance of 100 mW / cm 2 for 5 seconds, for a total irradiation amount of 500 mJ / cm 2 . It was.
　位置合わせ工程では、照射工程後の第１板を第２板の上方に配置して第１板と第２板の位置合わせをした。この場合、第１板の接着剤塗布面と第２板の上面とが対向するようにし、第１板と第２板とを平行に配置した。 In the alignment step, the first plate after the irradiation step was placed above the second plate to align the first plate and the second plate. In this case, the first plate and the second plate were arranged in parallel so that the adhesive application surface of the first plate and the upper surface of the second plate face each other.
　貼り合わせ工程では、位置合わせ工程後、未硬化の接着剤を介して第１板と第２板とを重ねて貼り合わせた。このとき、接着剤は、貼り合わせ時の圧力により、第１板と第２板の間にほぼ均等な厚みとなるように広がった。 In the bonding process, after the positioning process, the first plate and the second plate were overlapped and bonded via an uncured adhesive. At this time, the adhesive spread so as to have a substantially uniform thickness between the first plate and the second plate due to the pressure at the time of bonding.
　養生工程では、貼り合わせた第１板と第２板とを静置して接着剤を完全硬化させた。 In the curing process, the bonded first plate and second plate were allowed to stand to completely cure the adhesive.
　このようにして接着剤の硬化物である固定層で第１板と第２板とが接着されて固定された積層体が得られた。 Thus, a laminated body in which the first plate and the second plate were bonded and fixed by the fixing layer which was a cured product of the adhesive was obtained.
　［評価］
　上記のようにして得られた積層体について、以下の評価を行った。 [Evaluation]
The following evaluation was performed about the laminated body obtained as mentioned above.
　［全光透過率］
　固定層の全光透過率の評価方法は、ヘーズメーター（ＮＤＨ　４０００、日本電色工業株式会社製）により測定し、９０％以上を○、９０％未満を×と標記した。 [Total light transmittance]
The evaluation method of the total light transmittance of the fixed layer was measured with a haze meter (NDH 4000, manufactured by Nippon Denshoku Industries Co., Ltd.), and 90% or more was marked as ◯, and less than 90% as x.
　［厚み］
　固定層の厚みの評価方法は、積層体の厚みをダイヤルシックネスゲージ（ミツトヨ社製）で測定し、第１板と第２板の厚みを差し引くことで算出し、５０～２００μmを○、それ以外を×と標記した。 [Thickness]
The thickness of the fixed layer is evaluated by measuring the thickness of the laminate with a dial thickness gauge (manufactured by Mitutoyo Corporation) and subtracting the thicknesses of the first and second plates. Was marked as x.
　［密着性（密着強度）］
　表１に記載した各光カチオン重合組成物をプッシュアウト法にて接着強度を測定した。ＡＢＳ樹脂板Ａ上に４０ｍｍ角の枠状に線幅０．５ｍｍで塗布し、ＵＶ－ＬＥＤ光源（浜松ホトニクス株式会社製、ＬＣ－Ｌ２、中心波長３６５ｎｍ）を使用して紫外線を１００ｍＷ／ｃｍ２の照度で５秒間照射した。この後すみやかに、中心に２０ｍｍΦの穴を開けたＡＢＳ樹脂板ＢをＡＢＳ樹脂板Ａに貼り合せ、室温２５℃雰囲気下で１２時間養生して試験片を作成した。プッシュプルゲージの測定部をＡＢＳ樹脂板Ｂの穴を介してＡＢＳ樹脂板Ａに押し当て、ＡＢＳ樹脂板Ａに垂直方向の力をかけ、剥離するまでの最大応力を測定し、接着強度とした。なお、試験速度は１０ｍｍ／ｓｅｃとした。 [Adhesion (adhesion strength)]
The adhesive strength of each photocationic polymerization composition described in Table 1 was measured by a push-out method. It is coated on ABS resin plate A in a 40 mm square frame with a line width of 0.5 mm, and UV light is 100 mW / cm 2 using a UV-LED light source (Hamamatsu Photonics, LC-L2, center wavelength 365 nm). For 5 seconds. Immediately thereafter, an ABS resin plate B having a 20 mmφ hole in the center was bonded to the ABS resin plate A, and cured for 12 hours in an atmosphere at room temperature of 25 ° C. to prepare a test piece. The measurement part of the push-pull gauge is pressed against the ABS resin plate A through the hole of the ABS resin plate B, a vertical force is applied to the ABS resin plate A, and the maximum stress until peeling is measured to obtain the adhesive strength. . The test speed was 10 mm / sec.
　必要な接着強度は用途により様々であるが、ここでは４０Ｎ（１．０ＭＰａ）以上とし、６０Ｎ以上を◎、４０Ｎ以上６０Ｎ未満を○、４０Ｎ未満を×と表記した。 The required adhesive strength varies depending on the application. Here, it is 40N (1.0 MPa) or more, 60N or more is indicated by ◎, 40N or more and less than 60N is indicated by ○, and 40N or less is indicated by ×.
　［貯蔵弾性率］
　固定層の貯蔵弾性率の評価方法は、表１に記載した各光カチオン重合組成物を直径２０ｍｍ、厚み１ｍｍにくり貫いたシリコーンラバー中に流し込み、ＵＶ－ＬＥＤ光源を使用して紫外線を１００ｍＷ／ｃｍ２の照度で５秒間照射して作成した固形物を、レオメータを使用して、オシレーションモードにて２５℃、１Ｈｚの条件で測定した。ＵＶ－ＬＥＤ光源は、浜松ホトニクス株式会社製、ＬＣ－Ｌ２、中心波長３６５ｎｍを使用した。レオメータは、ＡＲ２０００ex、ＴＡインスツルメンツ社製を使用した。 [Storage modulus]
The storage elastic modulus of the fixed layer was evaluated by pouring each of the cationic photopolymerization compositions shown in Table 1 into a silicone rubber having a diameter of 20 mm and a thickness of 1 mm, and using an UV-LED light source to emit ultraviolet light at 100 mW / A solid material produced by irradiation for 5 seconds at an illuminance of cm 2 was measured using a rheometer in an oscillation mode at 25 ° C. and 1 Hz. As the UV-LED light source, LC-L2 manufactured by Hamamatsu Photonics Co., Ltd., center wavelength 365 nm was used. The rheometer used was AR2000ex, manufactured by TA Instruments.
　必要な貯蔵弾性率は用途及び構造により様々であるが、ここでは０．１ＭＰa以下を○、それより大きいものを×と標記した。 The required storage elastic modulus varies depending on the application and structure, but here, 0.1 MPa or less is marked with ○, and larger is marked with ×.
　［リワーク性］
　リワーク性の評価方法は、積層体の第２板から第１板を剥がした後、第２板の表層から表１に記載した各光カチオン重合組成物を竹串及びアルコール性の溶剤で除去可能かどうかで実施した。光カチオン重合組成物を除去できたものを○、出来なかったものを×と標記した。 [Reworkability]
The evaluation method of reworkability is that after removing the first plate from the second plate of the laminate, each photocationic polymerization composition described in Table 1 can be removed from the surface layer of the second plate with bamboo skewers and alcoholic solvents. It was carried out whether or not. Those in which the cationic photopolymerization composition could be removed were marked with ◯, and those that could not be made were marked with x.
　［黄変］
　黄変の評価方法は、積層体を８０℃の恒温槽に２５０時間投入し、表１に記載した各光カチオン重合組成物の固定層の変色を目視で確認した。目視で固定層を確認し、初期から変化ないものを○、初期から変化して黄変したものを×と標記した。 [Yellowing]
In the yellowing evaluation method, the laminate was put into a constant temperature bath at 80 ° C. for 250 hours, and the discoloration of the fixed layer of each photocationic polymerization composition described in Table 1 was visually confirmed. The fixed layer was visually confirmed, and those that did not change from the initial stage were marked with ◯, and those that changed from the initial stage and yellowed were marked with ×.
　［遅延硬化性］
　遅延硬化性の指標として、室温２５℃雰囲気下で紫外線照射後の粘度変化を用いて遅延時間を測定した。ＵＶ照射型レオメータ（株式会社アントンパール・ジャパン製、ＭＣＲ－１００）を用いて実施例及び比較例の各光カチオン重合組成物の紫外線照射前の粘度と照射後の粘度変化を測定した。紫外線の光源としてはＵＶ－ＬＥＤ光源（浜松ホトニクス株式会社製、ＬＣ－Ｌ２、中心波長３６５ｎｍ）を使用し、紫外線を１００ｍＷ／ｃｍ２の照度で５秒間照射し、合計５００ｍＪ／ｃｍ２の照射量とした。 [Delay curing]
As an indicator of delayed curability, the delay time was measured using the change in viscosity after UV irradiation at room temperature and 25 ° C. A UV irradiation type rheometer (manufactured by Anton Paar Japan Co., Ltd., MCR-100) was used to measure the viscosity of each of the photocationic polymerization compositions of Examples and Comparative Examples before ultraviolet irradiation and changes in viscosity after irradiation. Ultraviolet as a light source UV-LED light source (Hamamatsu Photonics Co., Ltd., LC-L2, the center wavelength of 365 nm) using a UV was irradiated for 5 seconds at an intensity of 100 mW / cm 2, irradiation amount of the total 500 mJ / cm 2 It was.
　遅延時間は、液状の光カチオン重合組成物への紫外線照射開始直後から光カチオン重合組成物の粘度が５００００Ｐａ・ｓに達するまでの時間とした。これは流動性がほとんど失われ、貼り合せが不可能になる粘度が５００００Ｐａ・ｓ程度であるためである。この遅延時間が１５秒以下では貼り合せるための猶予が少なく、６０分以上であれば、部材の位置ずれが起こる可能性が高くなる。 The delay time was defined as the time from immediately after the start of ultraviolet irradiation to the liquid photocationic polymerization composition until the viscosity of the photocationic polymerization composition reached 50000 Pa · s. This is because the fluidity is almost lost and the viscosity at which bonding becomes impossible is about 50000 Pa · s. If this delay time is 15 seconds or less, there is little time for pasting, and if it is 60 minutes or more, there is a high possibility that the member will be displaced.
　［耐ヒートサイクル性］
　耐ヒートサイクル性の評価方法は、積層体を－４０℃３０分と８０℃３０分とを交互に繰り返すヒートサイクル槽に投入した。そして、前述の温度サイクルを１サイクルとした際に、１００サイクル経過後の積層体に第１板と第２板及び固定層に剥離が生じていないかを確認した。剥離が生じていないものを○、生じたものを×と標記した。 [Heat cycle resistance]
In the evaluation method of heat cycle resistance, the laminate was put into a heat cycle tank where -40 ° C. for 30 minutes and 80 ° C. for 30 minutes were alternately repeated. And when the above-mentioned temperature cycle was made into 1 cycle, it was confirmed whether the 1st board, the 2nd board, and the fixed layer had peeled in the laminated body after 100 cycles progress. The case where peeling did not occur was marked with ◯, and the case where peeling occurred was marked with ×.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本実施形態は、以下の特徴を有する。 This embodiment has the following features.
　本実施形態の紫外線硬化性樹脂組成物は、多官能エポキシ化合物と、単官能エポキシ化合物と、多官能オキセタン化合物とを含む。前記紫外線硬化性樹脂組成物は、前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して、前記多官能エポキシ化合物及び前記多官能オキセタン化合物の含有量が合計で３０質量部以上９５質量部以下であり、前記単官能エポキシ化合物を７０質量部以下５質量部以上含有する。前記単官能エポキシ化合物は、炭素数７以上２０以下の炭化水素骨格の単官能エポキシ化合物を含有する。前記多官能エポキシ化合物及び前記単官能エポキシ化合物の少なくとも一方は、芳香族ベンゼン環含有エポキシ化合物を含有する。前記芳香族ベンゼン環含有エポキシ化合物の含有量は、前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して１質量部以上４０質量部以下である。 The ultraviolet curable resin composition of the present embodiment includes a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound. The ultraviolet curable resin composition contains the polyfunctional epoxy compound and the polyfunctional oxetane compound with respect to 100 parts by mass of the total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. The total amount is 30 parts by mass or more and 95 parts by mass or less, and the monofunctional epoxy compound is contained by 70 parts by mass or less and 5 parts by mass or more. The monofunctional epoxy compound contains a monofunctional epoxy compound having a hydrocarbon skeleton having 7 to 20 carbon atoms. At least one of the polyfunctional epoxy compound and the monofunctional epoxy compound contains an aromatic benzene ring-containing epoxy compound. Content of the said aromatic benzene ring containing epoxy compound is 1 to 40 mass parts with respect to 100 mass parts of total amounts of the said polyfunctional epoxy compound, the said monofunctional epoxy compound, and the said polyfunctional oxetane compound. .
　上記の紫外線硬化性樹脂組成物の硬化物で被着体を接着した場合に、積層体の層間の密着強度が高く、積層体の製造時のリワーク及び防汚性に優れる。 When the adherend is bonded with a cured product of the above-described ultraviolet curable resin composition, the adhesion strength between the layers of the laminate is high, and the rework and antifouling properties during the production of the laminate are excellent.
　本実施形態の紫外線硬化性樹脂組成物は、さらにエラストマーを含有することが好ましい。 The ultraviolet curable resin composition of the present embodiment preferably further contains an elastomer.
　この場合、エラストマーを含有していない紫外線硬化性樹脂組成物の硬化物に比べて、エラストマー中の極性基が被着体との化学的相互作用を強めたり、エラストマー中のカチオン重合性置換基が被着体との化学結合を形成するといった化学的物特性の変化が生じ、紫外線硬化性樹脂組成物の硬化物と被着体との密着性（接着強度）が向上する。 In this case, compared to the cured product of the ultraviolet curable resin composition not containing an elastomer, the polar group in the elastomer strengthens the chemical interaction with the adherend, or the cationically polymerizable substituent in the elastomer Changes in chemical properties such as formation of chemical bonds with the adherend occur, and adhesion (adhesive strength) between the cured product of the ultraviolet curable resin composition and the adherend is improved.
　本実施形態の積層体（３００）は、紫外線を透過しない第１板（３０）と、紫外線を透過しない第２板（３１）と、第１板（３０）と第２板（３１）と間に設けられ、第１板（３０）と第２板（３１）とを固定する固定層（３２）とを有する積層体（３００）である。固定層（３２）は、第１板（３０）と第２板（３１）の間に設けられて第１板（３０）と第２板（３１）とをリワーク可能に貼り合わせる紫外線硬化性樹脂組成物の硬化物である。前記紫外線硬化性樹脂組成物は、多官能エポキシ化合物と、単官能エポキシ化合物と、多官能オキセタン化合物とを含む。前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して、前記多官能エポキシ化合物及び前記多官能オキセタン化合物の含有量が合計で３０質量部以上９５質量部以下であり、前記単官能エポキシ化合物を７０質量部以下５質量部以上含有する。前記単官能エポキシ化合物は、炭素数７以上２０以下の炭化水素骨格の単官能エポキシ化合物を含有する。前記多官能エポキシ化合物及び前記単官能エポキシ化合物の少なくとも一方は、芳香族ベンゼン環含有エポキシ化合物を含有する。前記芳香族ベンゼン環含有エポキシ化合物の含有量は、前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して１質量部以上４０質量部以下である。 The laminated body (300) of this embodiment includes a first plate (30) that does not transmit ultraviolet light, a second plate (31) that does not transmit ultraviolet light, and a space between the first plate (30) and the second plate (31). And a laminated body (300) having a fixed layer (32) for fixing the first plate (30) and the second plate (31). The fixing layer (32) is an ultraviolet curable resin provided between the first plate (30) and the second plate (31) to bond the first plate (30) and the second plate (31) so that they can be reworked. It is a cured product of the composition. The ultraviolet curable resin composition includes a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound. The total content of the polyfunctional epoxy compound and the polyfunctional oxetane compound is 100 parts by mass or more with respect to 100 parts by mass of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. The amount of the monofunctional epoxy compound is 70 parts by mass or less and 5 parts by mass or more. The monofunctional epoxy compound contains a monofunctional epoxy compound having a hydrocarbon skeleton having 7 to 20 carbon atoms. At least one of the polyfunctional epoxy compound and the monofunctional epoxy compound contains an aromatic benzene ring-containing epoxy compound. Content of the said aromatic benzene ring containing epoxy compound is 1 to 40 mass parts with respect to 100 mass parts of total amounts of the said polyfunctional epoxy compound, the said monofunctional epoxy compound, and the said polyfunctional oxetane compound. .
　この場合、固定層（３２）による第１板（３０）と第２板（３１）の密着強度が高く、第１板（３０）と第２板（３１）の接着時のリワーク及び防汚性に優れる。 In this case, the adhesion strength between the first plate (30) and the second plate (31) by the fixed layer (32) is high, and rework and antifouling properties when the first plate (30) and the second plate (31) are bonded. Excellent.
　本実施形態の積層体では、第１板（３０）は、全光透過率が８５％以上の透明板であり、第２板（３１）は、第１板（３０）に平行に設けられた表示板であることが好ましい。 In the laminate of the present embodiment, the first plate (30) is a transparent plate having a total light transmittance of 85% or more, and the second plate (31) is provided in parallel to the first plate (30). A display board is preferred.
　この積層体が、スマートフォン又は携帯電話などの携帯用電子端末の表示装置である場合、固定層（３２）による第１板（３０）と第２板（３１）の密着強度が高く、第１板（３０）と第２板（３１）の接着時のリワーク及び防汚性に優れる。 When this laminated body is a display device of a portable electronic terminal such as a smartphone or a mobile phone, the first plate (30) and the second plate (31) with the fixed layer (32) have high adhesion strength, and the first plate It is excellent in rework and antifouling property when adhering (30) and the second plate (31).
　本実施形態の積層体では、固定層（３２）の全光透過率が８５％以上であることが好ましい。 In the laminate of the present embodiment, it is preferable that the total light transmittance of the fixed layer (32) is 85% or more.
　この積層体が、スマートフォン又は携帯電話などの携帯用電子端末の表示装置である場合、文字及び画像等の表示の視認性が固定層（３２）で損なわれにくい。 When this laminate is a display device of a portable electronic terminal such as a smartphone or a mobile phone, the visibility of display of characters, images and the like is not easily impaired by the fixed layer (32).
　本実施形態の積層体では、固定層（３２）の厚みが１０μｍ以上１０ｍｍ以下であることが好ましい。 In the laminate of the present embodiment, it is preferable that the thickness of the fixed layer (32) is 10 μm or more and 10 mm or less.
　この積層体が、スマートフォン又は携帯電話などの携帯用電子端末の表示装置である場合、厚くなりにくく、携帯性が損なわれにくい。 When this laminate is a display device of a portable electronic terminal such as a smartphone or a mobile phone, it is difficult to be thick and the portability is not easily lost.
　本実施形態の積層体では、固定層（３２）の貯蔵弾性率が０．１ＭＰａ以下であることが好ましい。 In the laminate of the present embodiment, it is preferable that the storage elastic modulus of the fixed layer (32) is 0.1 MPa or less.
　この積層体が、スマートフォン又は携帯電話などの携帯用電子端末の表示装置である場合、落下等による衝撃で第１板（３０）と第２板（３１）との接着が外れにくくなる。 When this laminate is a display device of a portable electronic terminal such as a smartphone or a mobile phone, the first plate (30) and the second plate (31) are hardly detached due to an impact caused by dropping or the like.
　本実施形態の積層体では、固定層（３２）と第２板（３１）との密着強度が１０Ｎ／ｃｍ２以上１５０Ｎ／ｃｍ２以下であることが好ましい。 In the laminated body of this embodiment, it is preferable that the adhesive strength between the fixed layer (32) and the second plate (31) is 10 N / cm 2 or more and 150 N / cm 2 or less.
　この積層板では、固定層（３２）から第２板（３１）が外しやすくなり、リワークに優れる。 In this laminate, the second plate (31) can be easily removed from the fixed layer (32), which is excellent for rework.
　３００　積層体
　３０　第１板
　３１　第２板
　３２　固定層
　３０１　透明板
　３１１　表示板
  300 Laminated body 30 First plate 31 Second plate 32 Fixed layer 301 Transparent plate 311 Display plate

Claims (8)

  1. 　多官能エポキシ化合物と、単官能エポキシ化合物と、多官能オキセタン化合物とを含み、
    　前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して、前記多官能エポキシ化合物及び前記多官能オキセタン化合物の含有量が合計で３０質量部以上９５質量部以下であり、前記単官能エポキシ化合物を７０質量部以下５質量部以上含有し、
    　前記単官能エポキシ化合物は、炭素数７以上２０以下の炭化水素骨格の単官能エポキシ化合物を含有し、
    　前記多官能エポキシ化合物及び前記単官能エポキシ化合物の少なくとも一方は、芳香族ベンゼン環含有エポキシ化合物を含有し、
    　前記芳香族ベンゼン環含有エポキシ化合物の含有量は、前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して１質量部以上４０質量部以下である
    　紫外線硬化性樹脂組成物。     A polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound;
    The total content of the polyfunctional epoxy compound and the polyfunctional oxetane compound is 100 parts by mass or more with respect to 100 parts by mass of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. The amount of the monofunctional epoxy compound is 70 parts by mass or less and 5 parts by mass or more.
    The monofunctional epoxy compound contains a monofunctional epoxy compound having a hydrocarbon skeleton having 7 to 20 carbon atoms,
    At least one of the polyfunctional epoxy compound and the monofunctional epoxy compound contains an aromatic benzene ring-containing epoxy compound,
    Content of the said aromatic benzene ring containing epoxy compound is 1 to 40 mass parts with respect to 100 mass parts of total amounts of the said polyfunctional epoxy compound, the said monofunctional epoxy compound, and the said polyfunctional oxetane compound. UV curable resin composition.
  2. 　請求項１において、
    　さらにエラストマーを含有する
    　紫外線硬化性樹脂組成物。     In claim 1,
    Further, an ultraviolet curable resin composition containing an elastomer.
  3. 　紫外線を透過しない第１板と、
    　紫外線を透過しない第２板と、
    　前記第１板と前記第２板と間に設けられ、前記第１板と前記第２板とを固定する固定層とを有する積層体であって、
    　前記固定層は、前記第１板と前記第２板の間に設けられて前記第１板と前記第２板とをリワーク可能に貼り合わせる紫外線硬化性樹脂組成物の硬化物であり、
    　前記紫外線硬化性樹脂組成物は、多官能エポキシ化合物と、単官能エポキシ化合物と、多官能オキセタン化合物とを含み、前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して、前記多官能エポキシ化合物及び前記多官能オキセタン化合物の含有量が合計で３０質量部以上９５質量部以下であり、前記単官能エポキシ化合物を７０質量部以下５質量部以上含有し、
    　前記単官能エポキシ化合物は、炭素数７以上２０以下の炭化水素骨格の単官能エポキシ化合物を含有し、
    　前記多官能エポキシ化合物及び前記単官能エポキシ化合物の少なくとも一方は、芳香族ベンゼン環含有エポキシ化合物を含有し、
    　前記芳香族ベンゼン環含有エポキシ化合物の含有量は、前記多官能エポキシ化合物と前記単官能エポキシ化合物と前記多官能オキセタン化合物との合計量１００質量部に対して１質量部以上４０質量部以下である
    　積層体。     A first plate that does not transmit ultraviolet light;
    A second plate that does not transmit ultraviolet light;
    A laminated body provided between the first plate and the second plate and having a fixing layer for fixing the first plate and the second plate;
    The fixed layer is a cured product of an ultraviolet curable resin composition that is provided between the first plate and the second plate and bonds the first plate and the second plate so that they can be reworked,
    The ultraviolet curable resin composition includes a polyfunctional epoxy compound, a monofunctional epoxy compound, and a polyfunctional oxetane compound, and a total amount of the polyfunctional epoxy compound, the monofunctional epoxy compound, and the polyfunctional oxetane compound. The total content of the polyfunctional epoxy compound and the polyfunctional oxetane compound is 30 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass, and the monofunctional epoxy compound contains 70 parts by mass or less and 5 parts by mass or more. And
    The monofunctional epoxy compound contains a monofunctional epoxy compound having a hydrocarbon skeleton having 7 to 20 carbon atoms,
    At least one of the polyfunctional epoxy compound and the monofunctional epoxy compound contains an aromatic benzene ring-containing epoxy compound,
    Content of the said aromatic benzene ring containing epoxy compound is 1 to 40 mass parts with respect to 100 mass parts of total amounts of the said polyfunctional epoxy compound, the said monofunctional epoxy compound, and the said polyfunctional oxetane compound. Laminated body.
  4. 　請求項３において、
    　前記第１板は、全光透過率が８５％以上の透明板であり、
    　前記第２板は、前記第１板に平行に設けられた表示板である
    　積層体。     In claim 3,
    The first plate is a transparent plate having a total light transmittance of 85% or more,
    The second plate is a display plate provided in parallel to the first plate.
  5. 　請求項３又は４において、
    　前記固定層の全光透過率が８５％以上である
    　積層体。     In claim 3 or 4,
    A laminate in which the total light transmittance of the fixed layer is 85% or more.
  6. 　請求項３乃至５のいずれか１項において、
    　前記固定層の厚みが１０μｍ以上１０ｍｍ以下である
    　積層体。     In any one of Claims 3 thru | or 5,
    A laminate having a thickness of the fixed layer of 10 μm or more and 10 mm or less.
  7. 　請求項３乃至６のいずれか１項において、
    　前記固定層の貯蔵弾性率が０．１ＭＰａ以下である
    　積層体。     In any one of Claims 3 thru | or 6,
    The laminated body whose storage elastic modulus of the said fixed layer is 0.1 Mpa or less.
  8. 　請求項３乃至７のいずれか１項において、
    　前記固定層と前記第２板との密着強度が１０Ｎ／ｃｍ２以上１５０Ｎ／ｃｍ２以下である
    　積層体。
          In any one of Claims 3 thru | or 7,
    A laminate having an adhesion strength between the fixed layer and the second plate of 10 N / cm 2 or more and 150 N / cm 2 or less.
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JPWO2019189154A1 (en) * 2018-03-27 2021-04-01 日本カーバイド工業株式会社 Manufacturing method of retroreflective sheet and retroreflective sheet
CN111902743B (en) * 2018-03-27 2022-10-04 日本电石工业株式会社 Method for producing retroreflective sheet, and retroreflective sheet
JP7352538B2 (en) 2018-03-27 2023-09-28 日本カーバイド工業株式会社 Manufacturing method of retroreflective sheet and retroreflective sheet
US11927779B2 (en) 2018-03-27 2024-03-12 Nippon Carbide Industries Co., Inc. Method for manufacturing retroreflective sheet and retroreflective sheet
JP2021012318A (en) * 2019-07-08 2021-02-04 日本カーバイド工業株式会社 Retroreflective sheet
JP7336900B2 (en) 2019-07-08 2023-09-01 日本カーバイド工業株式会社 retroreflective sheet
RU2750384C2 (en) * 2019-11-08 2021-06-28 Ирина Александровна Косырихина Method for strengthening protection and eliminating adverse factors of installation of an additional protective glass

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