WO2015190563A1 - タッチパネル用紫外線硬化型樹脂組成物、それを用いた貼り合せ方法及び物品 - Google Patents
タッチパネル用紫外線硬化型樹脂組成物、それを用いた貼り合せ方法及び物品 Download PDFInfo
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- WO2015190563A1 WO2015190563A1 PCT/JP2015/066898 JP2015066898W WO2015190563A1 WO 2015190563 A1 WO2015190563 A1 WO 2015190563A1 JP 2015066898 W JP2015066898 W JP 2015066898W WO 2015190563 A1 WO2015190563 A1 WO 2015190563A1
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- curable resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
Definitions
- the present invention relates to an ultraviolet curable resin composition for bonding at least two optical substrates and a method for producing an optical member using the same.
- a touch panel In recent years, display devices that allow screen input by attaching a touch panel to a display screen of a display device such as a liquid crystal display, a plasma display, or an organic EL display have been widely used.
- a glass plate or a resin film on which a transparent electrode is formed is bonded with a slight gap facing each other. If necessary, a transparent protection made of glass or resin is provided on the touch surface. It has a structure in which plates are bonded together.
- the touch panel and the display unit are bonded with an ultraviolet curable adhesive
- the cured film of the resin composition is too hard at the time of bonding, the cured resin is less likely to follow the substrate when the substrate is distorted.
- a problem occurs.
- a gap is generated between the substrate and the cured resin layer when cured after bonding, and the substrate and the cured product layer are peeled off, resulting in a decrease in yield.
- peeling occurs due to biting air or the like.
- Patent Document 1 discloses a technique for preventing this problem by a method of moving the pressing means on the substrate and spreading it out as a bonding method.
- a method of moving the pressing means on the substrate and spreading it out as a bonding method.
- a gap is generated between the substrate and the cured resin layer during curing after bonding, or due to the impact or environmental change described above. The problem of generating gaps will remain.
- Patent Document 2 discloses a technique for preventing the above-described peeling problem by using a resin composition having a high elongation rate and high adhesion.
- the components in the resin composition must be operated, and in order to satisfy the physical properties, the range in which the resin composition material and the component ratio in the composition can be adjusted is limited, It becomes difficult to ensure other physical properties such as elasticity.
- a resin having only a high elongation has a limited ability to follow the substrate, and it is difficult to sufficiently follow the substrate and prevent the generation of a gap during curing after bonding.
- peeling of the substrate cannot be effectively prevented only by adhesion. There was also a problem.
- the present invention can provide an optical member such as a display unit having good productivity, good curability and adhesion, and the cured resin layer follows the substrate, and the UV curable resin for touch panels that hardly generates voids.
- An object is to provide a composition.
- a resin composition used for bonding at least two optical substrates which is a liquid softening component (A), a solid softening component (B), a photopolymerizable oligomer (C), a photopolymerizable monomer (D), an ultraviolet curable resin composition for a touch panel comprising a photopolymerization initiator (E), wherein the mass ratio of the liquid softening component (A) and the solid softening component (B) is:
- An ultraviolet curable resin composition characterized by being in the range of 50.5: 49.5 to 99.9: 0.1.
- the softening point of the solid softening component (B) is 60 ° C. or higher, and the mass ratio of the liquid softening component (A) to the solid softening component (B) is 50.5: 49.5 to 99. 9: A range of 0.1 to 0.1, an ultraviolet curable resin composition.
- the photopolymerizable oligomer (C) is urethane (meth) acrylate, and the ultraviolet curable resin composition for a touch panel as described in (1) or (2) (4)
- Photopolymerizable oligomer ( (C) is a urethane (meth) acrylate having at least one skeleton selected from the group consisting of polypropylene / polybutadiene / hydrogenated polybutadiene / polyisoprene / hydrogenated polyisoprene.
- UV curable resin composition for touch panel (5)
- Monofunctional acrylate (A) is represented by the following formula (1)
- the ultraviolet curable resin composition for a touch panel according to any one of (1) to (4), which is represented by: (6)
- the liquid softening component (A) includes any one of a hydroxyl group-containing polymer, a liquid terpene resin, or both, as described in any one of (1) to (6) UV curable resin composition for touch panels.
- the photopolymerizable monomer (D) the following formula (3)
- the ultraviolet curable resin composition for a touch panel according to any one of (1) to (7), which comprises a monofunctional acrylate represented by the formula: (9)
- the photopolymerizable monomer (D) the following formula (4)
- the ultraviolet curable resin composition for a touch panel according to any one of (1) to (7), which comprises a monofunctional acrylate represented by the formula: (10)
- (11) A method for producing an optical member in which at least two optical substrates having the following steps 1 and 2 are bonded together.
- Step 1 An ultraviolet curable resin composition for a touch panel according to any one of (1) to (10) is applied to at least one optical substrate to form an application layer, and the application Step of obtaining an optical substrate having a cured product layer by irradiating the layer with ultraviolet rays (Step 2)
- the other optical substrate is bonded to the cured product layer of the optical substrate obtained in Step 1, Or the process (12) which bonds the hardened
- cured material layer obtained by the said process 1 exists in the optical base material side, and the optical base material side And the uncured part existing on the opposite side.
- Step 3 A step of irradiating the cured product layer having an uncured portion in the bonded optical substrate with ultraviolet rays to cure the cured product layer.
- the maximum illuminance in the range of 200 to 320 nm is 30 or less, assuming that the maximum illuminance in the range of 320 to 450 nm is 100.
- the maximum illuminance in the range of 200 to 320 nm is 10 or less when the maximum illuminance in the range of 320 to 450 nm is set to 100 for the ultraviolet rays irradiated to the ultraviolet curable resin composition in the step 1.
- the ultraviolet curable resin composition of this invention is demonstrated.
- the phrase “can be added to an ultraviolet curable resin composition used for optics” means that an additive that lowers the transparency of the cured product to an extent that it cannot be used for optics is not included.
- (meth) acrylate means either one or both of methacrylate and acrylate. The same applies to “(meth) acrylic acid” and the like.
- “Acrylate” represents only acrylate and excludes methacrylate.
- a cured sheet having a thickness after curing of 200 ⁇ m is prepared with the ultraviolet curable resin composition used in the present invention, a preferable average transmittance of the sheet with light having a wavelength of 400 to 800 nm is: At least 90%.
- the ultraviolet curable resin composition for a touch panel of the present invention is a resin composition used for bonding at least two optical substrates, and contains a liquid softening component (A).
- the liquid softening component (A) can be used without particular limitation as long as it is liquid at room temperature (25 ° C.).
- the liquid softening component (A) is not cross-linked by ultraviolet light, and is present between the cross-links of the photopolymerizable oligomer or photopolymerizable monomer, thereby providing flexibility and reducing the shrinkage rate. have.
- liquid softening component (A) examples include polymers, oligomers, phthalates, phosphates, glycols, citrates, and aliphatic dibasic esters that are compatible in the composition. , Fatty acid esters, epoxy plasticizers, castor oils, terpene resins, hydrogenated terpene resins, liquid terpenes, and the like.
- oligomer and polymer examples include polyisoprene skeleton, hydrogenated polyisoprene skeleton, polybutadiene skeleton, oligomer or polymer having hydrogenated polybutadiene skeleton or xylene skeleton and esterified product thereof, adipic acid ester oligomer, polybutene, and the like. be able to. From the viewpoint of transparency, hydrogenated terpene resins, hydrogenated polyisoprene, hydrogenated polybutadiene, polybutene, and liquid terpenes are preferable.
- the specific gravity of the liquid at 20 ° C. is preferably 0.93 or less
- the dielectric constant at 1 Hz is preferably 3.5 or less
- the iodine value is 400 The following is preferable.
- the liquid softening component (A) preferably has a viscosity of 0.01 to 100 Pa ⁇ s with a cone plate rheometer at 25 ° C. under atmospheric pressure.
- the ultraviolet curable resin composition for a touch panel of the present invention contains a solid softening component (B).
- the solid softening component (B) can be used without particular limitation as long as it is solid at room temperature (25 ° C.).
- the solid softening component (B) is not cross-linked by ultraviolet rays, is present between the cross-links of the photopolymerizable oligomer or photopolymerizable monomer, and sticks to the hardened product surface by arranging on the hardened product layer surface. Can be provided, and the effect of improving the adhesion improving function is exhibited.
- solid softening component (B) examples include polymers, oligomers, phthalates, phosphates, glycols, citrates, and aliphatic dibasic esters that are compatible in the composition. , Fatty acid esters, epoxy plasticizers, castor oils, terpene resins, hydrogenated terpene resins, liquid terpenes, and the like.
- oligomer and polymer examples include polyisoprene skeleton, hydrogenated polyisoprene skeleton, polybutadiene skeleton, oligomer or polymer having hydrogenated polybutadiene skeleton or xylene skeleton and esterified product thereof, adipic acid ester oligomer, polybutene, and the like. be able to. From the viewpoint of transparency, hydrogenated terpene resins, hydrogenated polyisoprene, hydrogenated polybutadiene, polybutene, and liquid terpenes are preferable.
- hydroxyl group-containing polymers such as hydrogenated polybutadiene contained in the side chain, and liquid terpene resins are particularly preferable.
- a softening point is 60 degreeC or more, and it is more preferable that it is 70 degreeC or more.
- the liquid softening component (A) and the solid softening component (B) are in a constant weight ratio.
- the ratio is usually 50.5: 49.5 to 99.9: 0.1.
- the softening point of the solid softening component (B) is generally correlated with the molecular weight of the solid softening component, and the softening point of the solid softening component (B) showing a softening point of 60 ° C or higher is 60 to 115 ° C.
- the mass ratio of the liquid softening component (A) to the solid softening component (B) is preferably 94.9 to 50.5: 49.5 to 5.1, and more preferably 89.9 to 50.5: 49.5 to 10.1.
- the mass ratio of the liquid softening component (A) to the solid softening component (B) is preferably 99.9 to 55. .5: 44.5 to 0.1, and more preferably 99.9 to 60.5: 39.5 to 0.1.
- the liquid softening component (A) has a greater weight ratio than the solid softening component (B), so that the elasticity of the cured resin layer in temporary curing or main curing can be significantly improved. it can. And since it has high elasticity in this way, even when stress generated by pressure / temperature change or contraction rate difference between the substrate and the resin composition is applied to the substrate, it can immediately follow and restore to the substrate Can do. In addition, since the cured resin layer follows the substrate even after curing after bonding, it is difficult for separation to occur, so that the yield can be improved.
- the weight ratio of the softening component in the ultraviolet curable resin composition is usually 5 to 40% by weight, preferably 10 to 35% by weight, in the solid softening component (B).
- the liquid softening component (A) is usually 10 to 70% by weight, preferably 20 to 60% by weight.
- the ultraviolet curable resin composition of the present invention contains a photopolymerizable oligomer (C).
- a photopolymerizable oligomer (C) in the ultraviolet curable resin composition of this invention,
- skeleton It is preferable to use one selected from the group consisting of (meth) acrylates having a polybutadiene skeleton.
- urethane (meth) acrylate is preferable from the viewpoint of adhesive strength, and has at least one skeleton selected from the group consisting of polybutadiene / hydrogenated polybutadiene / polyisoprene / hydrogenated polyisoprene from the viewpoint of moisture resistance. Urethane (meth) acrylate is more preferable.
- the urethane (meth) acrylate is obtained by reacting polyhydric alcohol, polyisocyanate and hydroxyl group-containing (meth) acrylate.
- polyhydric alcohol examples include polybutadiene glycol, hydrogenated polybutadiene glycol, polyisoprene glycol, hydrogenated polyisoprene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4 A cyclic skeleton such as butanediol, alkylene glycol having 1 to 10 carbon atoms such as 1,6-hexanediol, triol such as trimethylolpropane and pentaerythritol, tricyclodecane dimethylol, bis- [hydroxymethyl] -cyclohexane, etc.
- polycarbonate polyol for example, polycarbonate diol obtained by reaction of 1,6-hexanediol and diphenyl carbonate, etc.
- polyether polyol for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-modified bisphenol A, etc.
- the polyhydric alcohol is preferably propylene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, polyisoprene glycol, or hydrogenated polyisoprene glycol, and weight average molecular weight from the viewpoint of transparency and flexibility.
- Hydrogenated polybutadiene glycol is preferred from the viewpoints of discoloration such as heat-resistant coloring and compatibility.
- the upper limit of the weight average molecular weight at this time is not particularly limited, but is preferably 10,000 or less, and more preferably 5000 or less. Moreover, you may use together 2 or more types of polyhydric alcohol as needed.
- organic polyisocyanate examples include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl isocyanate.
- isophorone diisocyanate is preferable from the viewpoint of toughness.
- hydroxyl group-containing (meth) acrylates include hydroxy C2-C4 alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylol cyclohexyl mono ( A (meth) acrylate, a hydroxycaprolactone (meth) acrylate, a hydroxyl group terminal polyalkylene glycol (meth) acrylate, etc. can be used.
- hydroxy C2-C4 alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylol cyclohexyl mono ( A (meth) acrylate, a hydroxycaprolactone (meth) acrylate, a hydroxyl group terminal polyalkylene glycol (meth) acryl
- the reaction for obtaining the urethane (meth) acrylate is performed, for example, as follows. That is, the polyhydric alcohol is mixed with an organic polyisocyanate per equivalent of the hydroxyl group so that the isocyanate group is preferably 1.1 to 2.0 equivalent, more preferably 1.1 to 1.5 equivalent. Is preferably reacted at 70 to 90 ° C. to synthesize a urethane oligomer. Next, the hydroxy (meth) acrylate compound is mixed so that the hydroxyl group is preferably 1 to 1.5 equivalents per equivalent of the isocyanate group of the urethane oligomer, and reacted at 70 to 90 ° C. to react with the target urethane (meth). ) Acrylate can be obtained.
- the weight average molecular weight of the urethane (meth) acrylate is preferably about 7,000 to 100,000, and more preferably 10,000 to 60,000. When the weight average molecular weight is less than 7000, shrinkage increases, and when the weight average molecular weight is greater than 100,000, curability is poor.
- urethane (meth) acrylates can be used alone or in admixture of two or more.
- the weight ratio of urethane (meth) acrylate in the photocurable resin composition of the present invention is usually 5 to 90% by weight, preferably 10 to 50% by weight.
- the (meth) acrylate having the polyisoprene skeleton has a (meth) acryloyl group at the terminal or side chain of the polyisoprene molecule.
- (Meth) acrylates having a polyisoprene skeleton are available as UC-203, UC102, and UC-1 (manufactured by Kuraray Co., Ltd.).
- the (meth) acrylate having a polyisoprene skeleton preferably has a polystyrene-equivalent number average molecular weight of 1,000 to 50,000, more preferably about 25,000 to 45,000.
- the weight ratio of the (meth) acrylate having a polyisoprene skeleton in the photocurable resin composition of the present invention is usually 5 to 90% by weight, preferably 10 to 50% by weight.
- the ultraviolet curable resin composition of the present invention contains a photopolymerizable monomer (D).
- a photopolymerizable monomer (D) a (meth) acrylate having one (meth) acryloyl group in the molecule can be preferably used.
- the photopolymerizable monomer (D) excludes (meth) acrylate having urethane (meth) acrylate, polyisoprene or hydrogenated polyisoprene skeleton, (meth) acrylate having polybutadiene or hydrogenated polybutadiene skeleton ( (Meth) acrylate is shown.
- R 1 represents a hydrogen atom or CH 3 , and n represents an integer of 1 to 3
- the monofunctional acrylate represented by these can be used conveniently.
- the composition ratio of the ultraviolet curable resin composition is preferably 1 to 20% by weight of the monofunctional acrylate represented by the above formula (1), 5 to 90% by weight of the photopolymerizable oligomer (C),
- the photopolymerizable monomer (D) other than (1) is 5 to 90% by weight
- the photopolymerization initiator (E) is 0.1 to 5% by weight
- the other components are the balance.
- Examples of the monofunctional acrylate represented by the formula (1) in the ultraviolet curable resin composition of the present invention include 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, and the like. 2 or more may be used in combination as required.
- R 1 when n is 2 or less (particularly when n is 1 or less), R 1 is preferably a methyl group. When n is 3 or more, R 1 is preferably a hydrogen atom.
- a total carbon number of 2 or more is preferable because a resin composition with low volatility and low cloudiness can be obtained.
- n an integer of 2 to 4.
- the monofunctional acrylate represented by these is preferable.
- Examples of the monofunctional acrylate represented by the formula (2) include 4-hydroxybutyl acrylate, 3-hydroxypropyl acrylate, and 2-hydroxyethyl acrylate. Furthermore, 4-hydroxybutyl acrylate is particularly preferable from the viewpoint of low volatility. When a methacrylate resin is used, the curing rate tends to be slow, and when the resin composition is actually used, it takes time to cure, which is not preferable.
- the MOH / (MC + MB) is preferably 0.3 or less, particularly preferably 0.28 or less, and particularly preferably 0.25 or less.
- the monofunctional acrylate represented by the formula (1) that satisfies the condition is referred to as a low volatility / whitening-resistant acrylate.
- the content of the photopolymerizable monomer represented by the formula (1) is preferably 1 to 20% by weight, more preferably 2 to 10% by weight, and particularly preferably 5.5 to 8% by weight.
- the content of the component of formula (1) is less than 1%, the whitening resistance is lowered.
- the content is 20% by weight or more, bubbles may easily enter during bonding, or the compatibility with other components may deteriorate and the liquid may become cloudy.
- the ultraviolet curable resin composition contains a hydroxyl group-containing methacrylate because some of the properties such as a decrease in the curing rate and whitening resistance are adversely affected.
- the methacrylate having a hydroxyl group is contained, the content is preferably 10% by weight or less, particularly preferably 5% by weight or less.
- Specific examples of the (meth) acrylate having one (meth) acryloyl group in the molecule other than the photopolymerizable monomer represented by the formula (1) include isooctyl (meth) acrylate and isoamyl (meth) acrylate. , Lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, tridecyl (meth) acrylate, etc.
- alkyl (meth) acrylates benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acryloylmorpholine, phenylglycidyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl acrylate Relate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 1-adamantyl methacrylate, polypropylene oxide-modified nonylphenyl (meth) acrylate, (meth) acrylate having a cyclic skeleton such as dicyclopentadieneoxyethyl (meth) acrylate, and alkyl (
- a monofunctional acrylate represented by formula (4) is preferred, and from the viewpoint of adhesive strength, the following formula (4)
- the monofunctional acrylate represented by these is more preferable.
- isostearyl acrylate is more preferable from the viewpoints of low volatility, reactivity, and flexibility.
- the number of R 2 alkyl groups in the above formula (3) is defined as MR, and in the above formula (1)
- the resin composition preferably a resin composition containing both compounds such that MR / (MC + MB) (hereinafter referred to as a special ratio) is 5.5 or less, and particularly preferably 5 or less. preferable. Further, from the viewpoint of making the whitening resistance particularly excellent, the resin composition contains both compounds having the low volatility / whitening resistance acrylate and the special ratio of 5.5 or less. It is preferably 5 or less.
- composition of the present invention can contain (a (meth) acrylate other than a (meth) acrylate having one (meth) acryloyl group in the molecule) as long as the characteristics of the present invention are not impaired.
- a (meth) acrylate other than a (meth) acrylate having one (meth) acryloyl group in the molecule for example, tricyclodecane dimethylol di (meth) acrylate, dioxane glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, alkylene oxide modified bisphenol A type di (meth) acrylate Trimethylol C2-C10 alkanes such as caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate and ethylene oxide-modified phosphoric acid di (meth) acrylate, trimethylolpropane tri
- these (meth) acrylate monomer components can be used alone or in admixture of two or more at any ratio.
- the weight ratio of the photopolymerizable monomer (D) other than the above formula (1) in the photocurable transparent resin composition of the present invention is usually 5 to 90% by weight, preferably 10 to 50% by weight. When it is less than 5% by weight, the curability is poor, and when it is more than 90% by weight, shrinkage increases.
- the ratio (weight ratio) of the component (1) to the component (3) is preferably in the range of 1: 2 to 1:25, particularly in the range of 1: 3 to 1:15. preferable.
- epoxy (meth) acrylate can be used as long as the characteristics of the present invention are not impaired.
- Epoxy (meth) acrylate has a function of improving curability and improving the hardness and curing speed of a cured product. Any epoxy (meth) acrylate can be used as long as it is obtained by reacting a glycidyl ether type epoxy compound with (meth) acrylic acid, and preferably used epoxy (meth) acrylate.
- Examples of the glycidyl ether type epoxy compound to be obtained include diglycidyl ether of bisphenol A or its alkylene oxide adduct, diglycidyl ether of bisphenol F or its alkylene oxide adduct, diglycidyl of hydrogenated bisphenol A or its alkylene oxide adduct.
- Diglycidyl ether ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether of ether, hydrogenated bisphenol F or its alkylene oxide adduct Neopentyl glycol diglycidyl ether, butanediol diglycidyl ether hexanediol diglycidyl ether to, cyclohexanedimethanol diglycidyl ether, and polypropylene glycol diglycidyl ether.
- Epoxy (meth) acrylate is obtained by reacting these glycidyl ether type epoxy compounds with (meth) acrylic acid under the following conditions.
- (Meth) acrylic acid is reacted at a ratio of 0.9 to 1.5 mol, more preferably 0.95 to 1.1 mol, per 1 equivalent of epoxy group of the glycidyl ether type epoxy compound.
- the reaction temperature is preferably 80 to 120 ° C., and the reaction time is about 10 to 35 hours.
- a catalyst such as triphenylphosphine, TAP, triethanolamine, or tetraethylammonium chloride.
- paramethoxyphenol, methylhydroquinone or the like can be used as a polymerization inhibitor.
- An epoxy (meth) acrylate that can be suitably used in the present invention is a bisphenol A type epoxy (meth) acrylate obtained from a bisphenol A type epoxy compound.
- the weight average molecular weight of the epoxy (meth) acrylate is preferably 500 to 10,000.
- the weight ratio of the epoxy (meth) acrylate in the ultraviolet curable resin composition of the present invention is usually 1 to 80% by weight, preferably 5 to 30% by weight.
- the photopolymerization initiator (E) contained in the composition of the present invention is not particularly limited, and examples thereof include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylphenylethoxyphosphine.
- Fin oxide bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone ( Irgacure 184; manufactured by BASF), 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer (Esacure ONE; manufactured by Lamberti), 1- [4- (2-hydroxyethoxy) -phenyl ] -2-Hydroxy-2-methyl -1-propan-1-one (Irgacure 2959; manufactured by BASF), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl -Propan-1-one (Irgacure 127; manufactured by BASF), 2,2-dimethoxy-2-phen
- the molar extinction coefficient at 302 nm or 313 nm measured in acetonitrile or methanol is 300 ml / (g ⁇ cm) or more, and the molar extinction coefficient at 365 nm is 100 ml. It is preferable to use a photopolymerization initiator that is not more than / (g ⁇ cm). By using such a photopolymerization initiator, it is possible to contribute to an improvement in adhesive strength.
- the molar extinction coefficient at 302 nm or 313 nm is 300 ml / (g ⁇ cm) or more, curing at the time of curing in the following step 3 is sufficient.
- photopolymerization initiator (E) examples include 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173).
- these photopolymerization initiators (E) can be used alone or in admixture of two or more at any ratio.
- the weight ratio of the photopolymerization initiator (E) in the photocurable resin composition of the present invention is usually 0.2 to 5% by weight, preferably 0.3 to 3% by weight. When it is more than 5% by weight, when obtaining a cured product layer having a cured part and an uncured part on the side opposite to the optical substrate side, the uncured part cannot be formed or the transparency of the resin cured product layer is low. There is a risk of getting worse.
- the ultraviolet curable resin composition of the present invention can contain additives, which will be described later, as other components.
- amines that can serve as photopolymerization initiation assistants can be used in combination with the above photopolymerization initiator.
- examples of amines that can be used include benzoic acid 2-dimethylaminoethyl ester, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, and p-dimethylaminobenzoic acid isoamyl ester.
- the photopolymerization initiation assistant such as amines
- the content in the adhesive resin composition of the present invention is usually 0.005 to 5% by weight, preferably 0.01 to 3% by weight.
- an antioxidant In the ultraviolet curable resin composition of the present invention, an antioxidant, an organic solvent, a silane coupling agent, a polymerization inhibitor, a leveling agent, an antistatic agent, a surface lubricant, a fluorescent whitening agent, and a light stabilizer are optionally added. You may add additives, such as an agent (for example, hindered amine compound etc.) and a filler.
- an agent for example, hindered amine compound etc.
- antioxidants include, for example, BHT, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine Pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, , N-hexamethylenebis (3,5-di-di
- organic solvent examples include alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, toluene, xylene and the like.
- silane coupling agent examples include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, ⁇ -mercapropropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltri
- polymerization inhibitor examples include paramethoxyphenol and methylhydroquinone.
- the light stabilizer include, for example, 1,2,2,6,6-pentamethyl-4-piperidyl alcohol, 2,2,6,6-tetramethyl-4-piperidyl alcohol, 1,2,2, 6,6-pentamethyl-4-piperidyl (meth) acrylate (LA-82, manufactured by ADEKA Corporation), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3 4-butanetetracarboxylate, tetrakis (2,2,6,6-totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] Unde Mixed ester with decanoic acid bis (2,2,6,6-tetramethyl-4-
- the filler include, for example, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc and the like.
- examples thereof include powder or beads obtained by spheroidizing these.
- the weight ratio of the various additives in the photocurable transparent resin composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, more preferably 0.02 to 0.5% by weight.
- the ultraviolet curable resin composition of the present invention can be obtained by mixing and dissolving the aforementioned components at room temperature to 80 ° C., and if necessary, impurities may be removed by an operation such as filtration.
- impurities may be removed by an operation such as filtration.
- Step 1 By applying the ultraviolet curable resin composition to at least one optical substrate to form a coating layer, and irradiating the coating layer with ultraviolet rays, an optical group in the coating layer is formed.
- a cured portion (hereinafter referred to as “cured portion of the cured product layer” or simply “cured portion”) present on the material side (lower side of the coating layer) and the side opposite to the optical substrate side (upper side of the coating layer) Step of obtaining an optical substrate having a cured product layer having an uncured portion (hereinafter, referred to as “uncured portion of the cured product layer” or simply “uncured portion”) present on the atmosphere side.
- Step 1 there is no particular limitation on the curing rate of the coating layer after ultraviolet irradiation, and there is an uncured portion on the surface opposite to the optical substrate side (the upper side of the coating layer, usually the air side).
- Step 2 Another optical substrate is bonded to the uncured portion of the cured product layer of the optical substrate obtained in Step 1, or the other optical substrate obtained in Step 1 is cured. The process of bonding the uncured part of the material layer.
- FIG. 1 is a process diagram showing a first embodiment of a production process of an optical member using the ultraviolet curable resin composition of the present invention.
- This method is a method of obtaining an optical member by bonding the liquid crystal display unit 1 and the transparent substrate 2 together.
- the liquid crystal display unit 1 is a liquid crystal display unit in which a liquid crystal material is sealed between a pair of substrates on which electrodes are formed, and a polarizing plate, a driving circuit, a signal input cable, and a backlight unit are provided.
- the transparent substrate 2 is a transparent substrate such as a glass plate, a polymethyl methacrylate (PMMA) plate, a polycarbonate (PC) plate, an alicyclic polyolefin polymer (COP) plate, an acrylic resin, or polyethylene terephthalate.
- the transparent substrate may be subjected to hard coat treatment or antireflection treatment on one side or both sides.
- the transparent substrate 2 having a black frame-shaped light-shielding portion 4 on the surface of the transparent substrate can be preferably used, and the light-shielding portion 4 is formed by applying a tape, applying a paint, printing, or the like. In the present invention, the present invention can also be applied to a device that does not have the light shielding portion 4.
- transparent substrate having a light-shielding portion can be read as “transparent substrate”, and can be considered as an example in which the light-shielding portion is not provided as it is.
- an ultraviolet curable resin composition is apply
- the coating method include a slit coater, a roll coater, a spin coater, and a screen printing method.
- the ultraviolet curable resin composition applied to the surface of the liquid crystal display unit 1 and the transparent substrate 2 having the light shielding portion may be the same, or different ultraviolet curable resin compositions may be used. Usually, it is preferable that both are the same ultraviolet curable resin composition.
- the resin composition reaches the light shielding layer by filling the difference in height between the substrate and the light shielding layer.
- the film thickness of the cured product of each ultraviolet curable resin is adjusted so that the cured resin layer 7 after bonding has a thickness of 50 to 500 ⁇ m, preferably 50 to 350 ⁇ m, and more preferably 100 to 350 ⁇ m.
- the film thickness of the cured layer of the ultraviolet curable resin existing on the surface of the transparent substrate 2 having the light-shielding portion depends on the film thickness, the ultraviolet curable resin usually existing on the surface of the liquid crystal display unit 1 is used.
- the thickness is equal to or thicker than the thickness of the cured product layer of the mold resin. This is to minimize the portion that remains uncured even after irradiation with ultraviolet rays in Step 3 described later, thereby eliminating the risk of curing failure.
- the ultraviolet curable resin composition layer 5 after application is irradiated with ultraviolet rays 8 and a cured portion (in the drawing, the liquid crystal display unit side or the transparent substrate side as viewed from the ultraviolet curable resin composition) is present (in the figure). Curing with uncured parts (not shown in the figure) present on the upper side of the coating layer (on the opposite side of the liquid crystal display unit side or on the opposite side of the transparent substrate side) (on the atmospheric side when performed in the atmosphere) A physical layer 6 is obtained.
- the irradiation amount is preferably 5 to 2000 mJ / cm 2 , particularly preferably 10 to 1000 mJ / cm 2 .
- uncured refers to a fluid state in a 25 ° C. environment.
- the resin composition layer is touched with a finger after ultraviolet irradiation and a liquid component adheres to the finger, it is determined to have an uncured portion.
- any light source may be used as long as it is a lamp that irradiates ultraviolet to near ultraviolet rays.
- a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used.
- the wavelength of the ultraviolet ray irradiated to the ultraviolet curable resin composition is not particularly limited, but when the maximum illuminance in the range of 320 nm to 450 nm is 100, the ratio of the maximum illuminance at 200 to 320 nm.
- the (illuminance ratio) is preferably 30 or less, and particularly preferably the illuminance at 200 to 320 nm is 10 or less.
- the maximum illuminance in the range of 320 nm to 450 nm is 100, if the ratio of maximum illuminance (illuminance ratio) at 200 to 320 nm is higher than 30, the adhesive strength of the finally obtained optical member will be inferior. This is because if the illuminance at a low wavelength is high, the curing of the ultraviolet curable resin composition proceeds excessively at the time of curing in the step 1, and the contribution to the adhesion at the time of curing in the ultraviolet irradiation in the step 3 is reduced. This is thought to be due to this.
- the method of irradiating ultraviolet rays so as to achieve the above illuminance ratio includes, for example, a method of applying a lamp that satisfies the illuminance ratio as a lamp that irradiates ultraviolet to near ultraviolet rays, Even if the above condition is not satisfied, such illuminance can be obtained by using a base material (for example, a short wave ultraviolet cut filter, a glass plate, a film, etc.) that cuts short wavelength ultraviolet rays at the time of irradiation in step 1. Irradiation at a ratio is possible. Although it does not specifically limit as a base material which adjusts the illumination intensity ratio of an ultraviolet-ray, For example, the glass plate, soda-lime glass, PET film etc.
- irradiation with ultraviolet rays is usually carried out in the air at the upper surface on the coating side (on the opposite side of the liquid crystal display unit side or on the transparent substrate side as seen from the ultraviolet curable resin composition) (normal atmospheric surface) ). Further, ultraviolet irradiation may be performed while spraying a curing-inhibiting gas on the upper surface of the coating layer after evacuation.
- the side opposite to the liquid crystal display unit side or the side opposite to the transparent substrate side is the atmosphere side.
- ultraviolet rays may be irradiated in a vacuum environment or in a gas environment that does not cause hardening inhibition such as nitrogen.
- step 3 when step 3 is omitted, curing can be suitably performed in a vacuum or while spraying a gas (for example, nitrogen) that promotes curing. Thereby, even if the step 3 is omitted, sufficient adhesion can be performed.
- the state of the uncured portion and the film thickness of the uncured portion can be adjusted by spraying oxygen or ozone onto the surface of the ultraviolet curable resin layer (coating layer) during the ultraviolet irradiation. That is, when oxygen or ozone is sprayed on the surface of the coating layer, oxygen inhibition of curing of the ultraviolet curable resin composition occurs on the surface, so that the uncured portion of the surface can be ensured or the uncured portion
- the film thickness can be increased.
- the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 is irradiated with the ultraviolet-ray 8 from the transparent substrate 2 side which has a light-shielding part, and ultraviolet curable type
- the resin composition (coating layer) is cured.
- the dose of ultraviolet rays is preferably about 100 ⁇ 4000mJ / cm 2 in accumulated light quantity, particularly preferably 200 ⁇ 3000mJ / cm 2 approximately.
- the light source used for curing by irradiation with ultraviolet to near ultraviolet light may be any lamp as long as it is a lamp that emits ultraviolet to near ultraviolet light.
- a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used. In this way, an optical member as shown in FIG. 5 can be obtained.
- the optical member of the present invention may be manufactured by the second modified embodiment described below. Note that the details in each step are the same as those in the first embodiment, and therefore, the description of the same parts is omitted.
- the resin composition reaches the light shielding layer by filling the difference in height between the substrate and the light shielding layer.
- the wavelength of the ultraviolet ray irradiated to the ultraviolet curable resin composition is not particularly limited, but when the maximum illuminance in the range of 320 nm to 450 nm is 100, the ratio of the maximum illuminance at 200 to 320 nm is preferably 30 or less. Particularly preferably, the illuminance at 200 to 320 nm is 10 or less.
- the maximum illuminance in the range of 320 nm to 450 nm is 100, if the ratio of the maximum illuminance at 200 to 320 nm is higher than 30, the adhesive strength of the optical member finally obtained will be inferior.
- a transparent substrate 2 having a liquid crystal display unit 1 and a light shielding portion in a form in which the uncured portion of the obtained cured product layer 6 and the display surface of the liquid crystal display unit 1 face each other.
- Bonding can be performed either in air or in vacuum.
- FIG. 3 is a process diagram showing a third embodiment of a method for producing an optical member using the ultraviolet curable resin composition of the present invention. Note that the details in each step are the same as those in the first embodiment, and therefore, the description of the same parts is omitted. In addition, the same code
- the ultraviolet curable composition was applied to the surface of the liquid crystal display unit 1. Thereafter, the ultraviolet curable resin composition layer 5 is irradiated with ultraviolet rays 8, and the lower side 8 of the coating layer 8 and the cured portion present on the transparent substrate side as viewed from the ultraviolet curable resin composition, and the upper side of the coating layer ( A cured product layer 6 having an uncured portion present on the side opposite to the transparent substrate side is obtained.
- the wavelength of ultraviolet rays irradiated to the ultraviolet curable resin composition is not particularly limited, but when the maximum illuminance in the range of 320 nm to 450 nm is 100, the maximum illuminance at 200 to 320 nm is preferably 30 or less. The illuminance at 200 to 320 nm is preferably 10 or less. When the maximum illuminance in the range of 320 nm to 450 nm is 100, if the maximum illuminance at 200 to 320 nm is higher than 30, the adhesive strength of the finally obtained optical member will be inferior.
- the liquid crystal display unit 1 is formed such that the uncured portion of the obtained cured product layer 6 and the surface on which the light shielding portion on the transparent substrate 2 having the light shielding portion is formed face each other. And a transparent substrate 2 having a light shielding portion are bonded together. Bonding can be performed either in air or in vacuum.
- the optical member of the present invention may be manufactured by the following modified fourth embodiment. Note that the details in each step are the same as those in the first embodiment, and therefore, the description of the same parts is omitted.
- the fourth embodiment is described based on the second embodiment in which the step 3 is omitted, but the omission can be performed in the first to third embodiments.
- the resin composition reaches the light shielding layer by filling the difference in height between the substrate and the light shielding layer.
- the wavelength of the ultraviolet ray irradiated to the ultraviolet curable resin composition is not particularly limited, but when the maximum illuminance in the range of 320 nm to 450 nm is 100, the ratio of the maximum illuminance at 200 to 320 nm is preferably 30 or less. Particularly preferably, the illuminance at 200 to 320 nm is 10 or less.
- the maximum illuminance in the range of 320 nm to 450 nm is 100, if the ratio of the maximum illuminance at 200 to 320 nm is higher than 30, the adhesive strength of the optical member finally obtained will be inferior.
- some of the embodiments of the method for producing an optical member of the present invention are described with one specific optical base material.
- a liquid crystal display unit and a transparent substrate having a light shielding portion are used.
- various members described later as the optical base material can be used instead of the liquid crystal display unit, and various members described later as the optical base material are also used for the transparent substrate. be able to.
- an optical substrate such as a liquid crystal display unit and a transparent substrate
- these various members are further bonded to another optical substrate layer (for example, a film bonded with a cured layer of an ultraviolet curable resin composition). Or what laminated
- any method for adjusting the film thickness of the uncured portion by spraying nitrogen or ozone is not applied only to the above-described embodiment, but can be applied to any manufacturing method included in the present invention.
- the optical base material is an optical base material
- the optical base material bonded thereto is at least one display unit selected from the group consisting of a liquid crystal display unit, a plasma display unit, and an organic EL unit.
- One optical base material is a protective base material having a light-shielding part, and another optical base material bonded to it is a touch panel or a display unit having a touch panel, and at least two optical base materials are bonded.
- a mode in which the optical member is a touch panel having a protective base material having a light-shielding portion or a display unit having the same.
- the ultraviolet curable resin composition is applied to either the surface of the protective base material having the light shielding portion, the touch surface of the touch panel, or both of them. It is preferable to apply.
- One optical substrate is an optical substrate having a light-shielding portion, the other optical substrate bonded to it is a display unit, and an optical member having at least two optical substrates bonded thereto
- the aspect which is a display body unit which has an optical base material which has a light-shielding part.
- the ultraviolet curable resin is applied to either the surface of the optical substrate having the light shielding portion on the side where the light shielding portion is provided, the display surface of the display unit, or both of them. It is preferable to apply the composition.
- the optical substrate having a light shielding part include a display screen protective plate having a light shielding part, or a touch panel provided with a protective substrate having a light shielding part.
- the optical substrate having the light-shielding portion is a protective plate for a display screen having the light-shielding portion
- the surface of the optical substrate having the light-shielding portion is provided on the side on which the light-shielding portion is provided. It is the surface on the side where the part is provided.
- the optical substrate having the light shielding portion is a touch panel having a protective substrate having the light shielding portion
- the surface having the light shielding portion of the protective substrate having the light shielding portion is bonded to the touch surface of the touch panel.
- the surface of the optical substrate having the light shielding portion on the side where the light shielding portion is provided means the substrate surface of the touch panel opposite to the touch surface of the touch panel.
- the light-shielding part of the optical base material having the light-shielding part may be at any position of the optical base material, but is usually created in a frame shape around the optical base material in the form of a transparent plate or sheet, and its width is The thickness is about 0.5 mm to 10 mm, preferably about 1 to 8 mm, and more preferably about 2 to 8 mm.
- the ultraviolet curable resin composition of the present invention is produced by bonding at least two optical substrates by the above (Step 1) to (Step 2) and, if necessary, further (Step 3). Can be used in the way.
- the curing shrinkage of the cured product of the ultraviolet curable resin composition of the present invention is preferably 4.0% or less, and particularly preferably 3.0% or less.
- the transmittance at 400 nm to 800 nm of the cured product of the ultraviolet curable resin composition of the present invention is preferably 90% or more. This is because when the transmittance is less than 90%, it is difficult for light to pass therethrough and the visibility is lowered when used in a display device. Further, when the cured product has a high transmittance at 400 to 450 nm, the visibility can be further improved. Therefore, the transmittance at 400 to 450 nm is preferably 90% or more.
- the ultraviolet curable resin composition of the present invention can be suitably used as an adhesive for producing an optical member by laminating a plurality of optical substrates by the above (Step 1) to (Step 3).
- the optical substrate used in the method for producing an optical member of the present invention include a transparent plate, a sheet, a touch panel, and a display unit.
- the “optical substrate” means both an optical substrate having no light shielding part on the surface and an optical substrate having a light shielding part on the surface.
- at least one of a plurality of optical base materials used is an optical base material having a light shielding portion. The position of the light shielding part in the optical substrate having the light shielding part is not particularly limited.
- a band-shaped light shielding portion having a width of 0.05 to 20 mm, preferably about 0.05 to 10 mm, more preferably about 0.1 to 6 mm is formed in the peripheral portion of the optical substrate.
- the light-shielding portion on the optical substrate can be formed by attaching a tape, applying a coating or printing.
- Various materials can be used as the material of the optical substrate used in the present invention. Specifically, resins such as PET, PC, PMMA, a composite of PC and PMMA, glass, COC, COP, plastic (such as acrylic resin), and the like can be given.
- an optical substrate used in the present invention for example, a transparent plate or sheet, a sheet or transparent plate obtained by laminating a plurality of films or sheets such as polarizing plates, a non-laminated sheet or transparent plate, and a transparent made from inorganic glass Plates (inorganic glass plates and processed products thereof, such as lenses, prisms, ITO glass) and the like can be used.
- the optical substrate used in the present invention is a laminate composed of a plurality of functional plates or sheets (hereinafter referred to as “functional laminate”) such as a touch panel (touch panel input sensor) or the following display unit in addition to the polarizing plate described above. Also called “body”).
- Examples of the sheet that can be used as the optical substrate used in the present invention include an icon sheet, a decorative sheet, and a protective sheet.
- Examples of the plate (transparent plate) that can be used in the method for producing an optical member of the present invention include a decorative plate and a protective plate.
- materials for these sheets or plates those listed as materials for transparent plates can be applied.
- Examples of the material of the touch panel surface that can be used as the optical substrate used in the present invention include glass, PET, PC, PMMA, a composite of PC and PMMA, COC, and COP.
- the thickness of a plate-like or sheet-like optical substrate such as a transparent plate or a sheet is not particularly limited, and is usually about 5 ⁇ m to 5 cm, preferably about 10 ⁇ m to 10 mm, more preferably about 50 ⁇ m to 3 mm. Is the thickness.
- a plate-shaped or sheet-shaped transparent optical base material having a light-shielding portion and the functional laminate are cured products of the ultraviolet curable resin composition of the present invention.
- the optical member bonded together can be mentioned.
- a display unit with an optical functional material by using a display unit such as a liquid crystal display device as one of optical substrates and an optical functional material as another optical substrate ( Hereinafter, it is also referred to as a display panel).
- the display unit include display devices such as LCD, EL display, EL illumination, electronic paper, and plasma display in which a polarizing plate is attached to glass.
- the optical functional material include transparent plastic plates such as acrylic plates, PC plates, PET plates, and PEN plates, tempered glass, and touch panel input sensors.
- the refractive index of the cured product is 1.45 to 1.55 in order to improve the visibility because the visibility of the display image is further improved.
- the difference in refractive index from the base material used as the optical base material can be reduced, and the light loss can be reduced by suppressing the irregular reflection of light.
- Preferred embodiments of the optical member obtained by the production method of the present invention include the following (i) to (vii).
- An optical base selected from the group consisting of a transparent glass substrate having a light shielding part, a transparent resin substrate having a light shielding part, and a glass substrate on which a light shielding material and a transparent electrode are formed, as the optical base material having the light shielding part.
- the optical member according to (i), which is a material and the functional laminate is a display unit or a touch panel.
- a touch panel or touch panel input sensor in which a plate-shaped or sheet-shaped optical substrate having a light-shielding portion is bonded to the surface on the touch surface side of the touch panel using the cured product of the ultraviolet curable resin composition of the present invention.
- a display panel in which a plate-like or sheet-like optical substrate having a light-shielding portion is bonded onto the display screen of the display unit using the cured product of the ultraviolet curable resin composition of the present invention.
- the ultraviolet curable resin composition of the present invention By using the ultraviolet curable resin composition of the present invention and bonding a plurality of optical substrates selected from the above optical substrates by the method described in (Step 1) to (Step 3), The optical member of the invention is obtained.
- the ultraviolet curable resin composition may be applied to only one of the surfaces facing each other through the cured product layer in the two optical substrates to be bonded, or may be applied to both surfaces. good.
- the functional laminate is a touch panel or a display unit
- any one surface of the protective base material having a light shielding part, preferably the light shielding part is provided.
- the resin composition may be applied to only one of the provided surface and the touch surface of the touch panel or the display surface of the display unit, or may be applied to both of them.
- a light shielding portion of the protective base material is provided in Step 1, in which a protective base material or a touch panel for protecting the display screen of the display body unit is bonded to the display body unit.
- the resin composition may be applied to only one of the substrate surface opposite to the surface or the touch surface of the touch panel and the display surface of the display unit, or to both of them.
- the optical member including the display unit knit obtained by the manufacturing method of the present invention and the optical base material having the light shielding portion can be incorporated into an electronic device such as a television, a small game machine, a mobile phone, and a personal computer.
- Synthesis example 1 To a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 manufactured by Nippon Soda Co., Ltd. (iodine value: 12.2, hydroxyl value: 46.8 mg ⁇ KOH) as a hydrogenated polybutadiene polyol compound / G) is 569.73 g (0.24 mol), 7.50 g (0.0024 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g) manufactured by Asahi Glass Co., Ltd. as a diol compound is polymerizable.
- GI-2000 manufactured by Nippon Soda Co., Ltd.
- Synthesis example 2 To a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 manufactured by Nippon Soda Co., Ltd. (iodine value: 12.2, hydroxyl value: 46.8 mg ⁇ KOH) as a hydrogenated polybutadiene polyol compound / G) is 545.99 g (0.23 mol), 7.19 g (0.0023 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g) manufactured by Asahi Glass Co., Ltd. as a diol compound is polymerizable.
- GI-2000 manufactured by Nippon Soda Co., Ltd.
- Synthesis example 3 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, as a hydrogenated polybutadiene polyol compound, KRASOL HLBH-P 2000 (iodine value: 13.5, hydroxyl value: 0.89 meq / g) manufactured by CRAY VALLEY 511.69 g (0.23 mol), 7.19 g (0.0023 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g) manufactured by Asahi Glass Co., Ltd.
- KRASOL HLBH-P 2000 iodine value: 13.5, hydroxyl value: 0.89 meq / g
- Exenol 3020 polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g
- Example 1 20 parts by mass of the polyurethane compound (E-1) of Synthesis Example 1, 22 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation, 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI-2000 manufactured by Nippon Soda Co., Ltd.
- S-1800A isostearyl acrylate
- Bremer LA laauryl acrylate
- Clearon M-105 aromatically modified hydrogenated terpene resin
- LV-100 polybutene manufactured by JX Nippon Oil & Energy Corporation
- GI-2000 manufactured by Nippon Soda Co., Ltd.
- Example 2 20 parts by mass of the polyurethane compound (E-2) of Synthesis Example 2, 22 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation, Yashara Chemical Co., Ltd. Clearon M-105 (aromatically modified hydrogenated terpene resin) 18 parts by mass, JX Nippon Oil & Energy Corporation LV-100 (polybutene) 10 parts by mass, Nippon Soda Co., Ltd.
- S-1800A isostearyl acrylate
- Bremer LA laauryl acrylate
- Clearon M-105 aromatically modified hydrogenated terpene resin
- JX Nippon Oil & Energy Corporation LV-100 polybutene
- GI-2000 (1,2-hydrogenated polybutadiene glycol) 20 parts by mass
- LAMBSON speed cure TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) 0.5 parts by mass
- BASF IRGACURE184 (1-hydroxycyclohexylphenyl) Ketone
- PBD (2- (4-Bifeni) manufactured by Wako Pure Chemical Industries Lu) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (0.05 parts by mass) was heated to 70 ° C. and mixed to obtain a resin composition of the present invention.
- the viscosity of the composition was 5000 mPa ⁇ s.
- Example 3 20 parts by mass of the polyurethane compound (E-3) of Synthesis Example 3, 22 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation, 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI-2000 manufactured by Nippon Soda Co., Ltd.
- S-1800A isostearyl acrylate
- Bremer LA laauryl acrylate
- Clearon M-105 aromatically modified hydrogenated terpene resin
- LV-100 polybutene manufactured by JX Nippon Oil & Energy Corporation
- GI-2000 manufactured by Nippon Soda Co., Ltd.
- Examples 1 to 3 are shown in Table 1, and the following evaluation was performed.
- the refractive index (25 ° C.) of the resin was measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).
- Example 4 20 parts by mass of the polyurethane compound (E-1) of Synthesis Example 1, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation, 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI-2000 manufactured by Nippon Soda Co., Ltd. (1,2-hydrogenated polybutadiene glycol) 20 parts by mass, Osaka Organic Chemical Co., Ltd.
- Example 5 20 parts by mass of the polyurethane compound (E-2) of Synthesis Example 2, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation, 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI-2000 manufactured by Nippon Soda Co., Ltd. (1,2-hydrogenated polybutadiene glycol) 20 parts by mass, Osaka Organic Chemical Co., Ltd.
- Example 6 20 parts by mass of the polyurethane compound (E-3) of Synthesis Example 3, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation, 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, T-5562 manufactured by Asahi Kasei Chemicals Corporation (Polycarbonate polyol) 20 parts by mass, Osaka Organic Chemical Co., Ltd.
- S-1800A isostearyl acrylate
- Bremer LA laauryl acrylate
- Clearon M-105 aromatically modified hydrogenated terpene resin
- LV-100 polybutene
- T-5562 manufactured by Asahi Kasei Chemical
- Examples 4 to 6 are shown in Table 2 and evaluated as follows.
- the refractive index (25 ° C.) of the resin was measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).
- Two slide glasses having a thickness of 1 mm were prepared, and applied to one slide glass so that the film thickness of Examples 4 to 6 was 200 ⁇ m, and the other slide glass was bonded to the coated surface. Thereafter, the composition was irradiated with ultraviolet rays having a cumulative light amount of 4000 mJ / cm 2 through a glass with a high-pressure mercury lamp (80 W / cm, with an ozone-less / IR cut filter). The obtained test piece was placed in an environment of 80 ° C. and 85% RH for 48 hours, and then the state of the film 15 minutes after removal into the 25 ° C. and 45% RH environment, and the state of the cured film 3 hours after removal. It was confirmed visually.
- the film thickness of Examples 4-6 might be set to 200 micrometers on the slide glass of thickness 1mm, and peeling PET film was bonded together on the application surface. Thereafter, the composition was irradiated with ultraviolet rays having an integrated light amount of 4000 mJ / cm 2 through a peeled PET film with a high-pressure mercury lamp (80 W / cm, with ozone-less / IR cut filter). The obtained joined body was put in an environment of 80 ° C. and 85% RH for 48 hours, and then the state of the film 15 minutes after being taken out in the environment of 25 ° C. and 45% RH, and the state of the cured film 3 hours after being taken out. It was confirmed visually. As a result of the evaluation, the compositions of Examples 4 to 6 were all “good”.
- Adhesive strength 1 After a PET film and a glass plate having a thickness of 1 mm were bonded so that the film thickness after curing in Examples 1 to 6 was 200 ⁇ m, a high-pressure mercury lamp (80 W / cm, ozoneless / The composition was irradiated with ultraviolet rays having an integrated light amount of 4000 mJ / cm 2 with an IR cut filter. Adhesiveness was measured by the method based on JISZ0237 using the obtained joined body. Necessary for stripping the joined body of PET film and 1 mm thick glass plate horizontally so that the PET film is on the top surface, and peeling vertically from the end of the PET film (90 ° upward) The force was measured. The evaluation result and the determination result were both “good”. .
- Adhesive strength of 6.0 N / cm or more Adhesive strength of 1.5 N / cm or more and less than 6.0 N / cm ⁇ : Adhesive strength of less than 1.5 N / cm
- a glass joined body was obtained in accordance with the following experimental example.
- Experimental Example 1 Two glass plates having a size of width 2 cm ⁇ length 3.5 cm ⁇ thickness 1 mm were prepared, and the composition C was formed into a circle having a thickness of 200 ⁇ m and a diameter of 1 cm in the center of one of the glass plates. It was applied to. Thereafter, an electrodeless ultraviolet lamp (D-bulb manufactured by Heraeus Noblelight Fusion Ubuy Co., Ltd.) is used for the obtained coating layer, and the accumulated light quantity is 100 mJ from the atmosphere through an ultraviolet cut filter that blocks a wavelength of 320 nm or less.
- D-bulb manufactured by Heraeus Noblelight Fusion Ubuy Co., Ltd.
- a cured product layer having a cured portion present on the lower side (glass plate side) of the coating layer and an uncured portion present on the upper side (atmosphere side) of the coating layer.
- the ratio of the maximum illuminance in the range of 200 to 320 nm was 3 when the maximum illuminance in the range of 320 to 450 nm was 100 for the ultraviolet rays irradiated to Examples 1 to 6 at this time.
- the uncured portion existing on the upper side (atmosphere side) of the coating layer and the other glass plate are bonded in a cross shape (direction crossing 90 ° C.), and the accumulated light amount is 2000 mJ / over through the bonded glass.
- the cured resin layer was cured by irradiating cm 2 ultraviolet rays to obtain a joined body.
- Experimental example 2 Except that the ultraviolet cut filter that blocks the wavelength of 320 nm or less is changed to a glass plate having a thickness of 0.5 mm, it exists on the lower side (glass plate side) of the coating layer in the same manner as in Experimental example 1.
- a cured product layer having a cured portion and an uncured portion existing on the upper side (atmosphere side) of the coating layer was formed.
- the ratio of the maximum illuminance in the range of 200 to 320 nm was 21 when the maximum illuminance in the range of 320 to 450 nm was set to 100 for the ultraviolet rays irradiated to Examples 1 to 6 at this time.
- the uncured portion existing on the upper side (atmosphere side) of the coating layer and the other glass plate are bonded in a cross shape (direction crossing 90 ° C.), and the accumulated light amount is 2000 mJ / over through the bonded glass.
- the cured resin layer was cured by irradiating cm 2 ultraviolet rays to obtain a joined body.
- Experimental Example 3 A cured portion present on the lower side (glass plate side) of the coating layer and the upper side of the coating layer in the same manner as in Experimental Example 1 except that an ultraviolet cut filter that blocks a wavelength of 320 nm or less was not used. A cured product layer having an uncured portion existing on the (atmosphere side) was formed. At this time, the ratio of the maximum illuminance in the range of 200 to 320 nm was 45 when the maximum illuminance in the range of 320 to 450 nm was 100.
- the uncured portion existing on the upper side (atmosphere side) of the coating layer and the other glass plate are bonded in a cross shape (direction crossing 90 ° C.), and the accumulated light amount is 2000 mJ / over through the bonded glass.
- the cured resin layer was cured by irradiating cm 2 ultraviolet rays to obtain a joined body.
- Experimental Example 4 Using an applicator, the composition C was coated on a 100 mm ⁇ 100 mm ⁇ 100 ⁇ m thick 100 ⁇ m peeled PET film so that the thickness of the composition C was 200 ⁇ m, and then a 25 ⁇ m thick peeled PET film. Covered with.
- the composition C was cured by irradiating an ultraviolet ray with an accumulated light amount of 2000 mJ / cm 2 using an electrodeless ultraviolet lamp (D bulb, manufactured by Heraeus Noble Light Fusion Ubuy Co., Ltd.).
- a transparent adhesive sheet was obtained.
- the pressure-sensitive adhesive sheet was cut into a circle having a diameter of 1 cm, and then the peeled PET film having a thickness of 100 ⁇ m was peeled off.
- the rubber sheet having a mass of 1 kg and a width of 20 mm was reciprocated once so that the transparent adhesive sheet from which the peeled PET film had been peeled was attached to the center of a glass plate having a size of 2 cm wide ⁇ 3.5 cm long ⁇ 1 mm thick. .
- the peeled PET film having a thickness of 25 ⁇ m is peeled off, and a glass sheet having a width of 2 cm ⁇ length of 3.5 cm ⁇ thickness of 1 mm is bonded to a transparent adhesive sheet in a cross shape (direction crossing 90 ° C.).
- the ultraviolet curable resin composition and the production method of the present invention have good curability, high whitening resistance, strong adhesion to the base material, and are directly applied to the base material to be bonded. Then, it can be seen that it has a high adhesive force even when it is cured by irradiating ultraviolet rays and the other substrate is bonded.
- Two slide glasses having a thickness of 1 mm coated with a fluorine-based release agent were prepared, and the composition was applied to one of the release agent application surfaces so that the film thickness was 200 ⁇ m. That word, two slide glasses were bonded together so that the respective release agent application surfaces face each other.
- the resin composition was cured by irradiating the resin composition with ultraviolet rays having an accumulated light amount of 2000 mJ / cm 2 through a glass with a high-pressure mercury lamp (80 W / cm, ozone-less). Thereafter, the two slide glasses were peeled off to produce a cured product for measuring the film specific gravity. Based on JIS K7112 B method, specific gravity (DS) of hardened
- a slide glass with a thickness of 0.8 mm and an acrylic plate with a thickness of 0.8 mm were prepared, and after applying the composition obtained on one side so that the film thickness was 200 ⁇ m, the other was bonded to the application surface. .
- the resin composition was irradiated with ultraviolet rays having an integrated light quantity of 2000 mJ / cm 2 with a high-pressure mercury lamp (80 W / cm, ozone-less), and the resin composition was cured to prepare a sample for evaluating adhesiveness. This was left to stand at 85 ° C. and 85% RH for 250 hours. In the sample for evaluation, peeling of the slide glass or the acrylic plate from the cured resin was visually confirmed, but there was no peeling.
- the obtained composition was fully cured, and the durometer E hardness was measured using a durometer hardness meter (type E) by a method based on JIS K7215 to evaluate the flexibility. More specifically, the ultraviolet curable resin composition was poured into a cylindrical mold so that the film thickness was 1 cm, and the resin composition was sufficiently cured by irradiation with ultraviolet rays. The hardness of the obtained cured product was measured with a durometer hardness meter (type E). As a result, the measured value was less than 10, and the flexibility was excellent.
- the transmittance in the wavelength region of 400 to 800 nm and 400 to 450 nm was measured using a spectrophotometer (U-3310, Hitachi High-Technologies Corporation). As a result, the transmittance at 400 to 800 nm was 90% or more, and the transmittance at 400 to 450 nm was 90% or more.
- the composition is applied to each substrate on the display surface of the liquid crystal display unit having an area of 3.5 inches and the surface on which the light-shielding portion on the transparent substrate having the light-shielding portion (width 5 mm) is formed on the outer periphery. It applied so that it might become.
- an electrodeless ultraviolet lamp (D bulb, manufactured by Heraeus Noblelight Fusion Ubuy Co., Ltd.) was used for the obtained coating layer, and the accumulated light quantity from the atmosphere side was 100 mJ /
- a cured product layer having a cured portion and an uncured portion existing on the atmosphere side was formed by performing ultraviolet irradiation of cm 2 .
- the ratio of the maximum illuminance in the range of 200 to 320 nm was 3 when the maximum illuminance in the range of 320 to 450 nm was 100.
- a liquid crystal display unit and a transparent substrate having a light-shielding portion were bonded together with the uncured portions facing each other.
- the resin cured product layer is cured by irradiating UV light with an integrated light amount of 2000 mJ / cm 2 from the glass substrate side having the light shielding portion with an ultra-high pressure mercury lamp (TOSCURE752, manufactured by Harrison Toshiba Lighting Co., Ltd.). Produced.
- the transparent substrate was removed from the obtained optical member, and the cured resin layer of the light shielding part was washed away with heptane, and then the cured state was confirmed. There was no evidence that the uncured resin composition was removed, and the resin in the light shielding portion was sufficiently cured.
- 1 liquid crystal display unit 2 transparent substrate having a light shielding part, 3 transparent substrate, 4 light shielding part, 5 ultraviolet curable resin composition (ultraviolet curable resin composition), 6 cured material layer having an uncured part, 7 resin curing Material layer, 8 UV
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Cited By (4)
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WO2016163153A1 (ja) * | 2015-04-09 | 2016-10-13 | 協立化学産業株式会社 | 光硬化型接着組成物 |
WO2019069872A1 (ja) * | 2017-10-04 | 2019-04-11 | 日本化薬株式会社 | 紫外線硬化型接着剤組成物、その硬化物および紫外線硬化型接着剤組成物を用いた光学部材の製造方法 |
WO2021251437A1 (ja) * | 2020-06-12 | 2021-12-16 | 日東電工株式会社 | 粘着剤組成物、粘着剤層、粘着シート、光学部材、及びタッチパネル |
CN114456768A (zh) * | 2022-02-28 | 2022-05-10 | 杭州科望特种油墨有限公司 | 一种光固化液体胶膜组合物及其应用 |
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KR102071023B1 (ko) * | 2017-09-27 | 2020-01-29 | 동우 화인켐 주식회사 | 터치 센서 및 이의 제조방법 |
CN111249992A (zh) * | 2018-12-03 | 2020-06-09 | 沈欣 | 液态珠丸的制造方法 |
JP7092247B1 (ja) * | 2021-09-24 | 2022-06-28 | Agc株式会社 | 積層体、及び積層体の製造方法 |
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- 2015-06-11 KR KR1020167034658A patent/KR20170020346A/ko not_active Application Discontinuation
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WO2019069872A1 (ja) * | 2017-10-04 | 2019-04-11 | 日本化薬株式会社 | 紫外線硬化型接着剤組成物、その硬化物および紫外線硬化型接着剤組成物を用いた光学部材の製造方法 |
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JPWO2019069872A1 (ja) * | 2017-10-04 | 2020-09-10 | 日本化薬株式会社 | 紫外線硬化型接着剤組成物、その硬化物および紫外線硬化型接着剤組成物を用いた光学部材の製造方法 |
CN111164170B (zh) * | 2017-10-04 | 2022-07-05 | 日本化药株式会社 | 紫外线硬化型粘合剂组合物、其硬化物及使用紫外线硬化型粘合剂组合物的光学构件的制造方法 |
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