Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
  • C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
• • 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
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • 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
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
  • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
• • 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
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
  • B32B2457/202—LCD, i.e. liquid crystal displays
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
  • B32B2457/208—Touch screens
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/26—Esters of unsaturated alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F2202/00—Materials and properties
  • G02F2202/28—Adhesive materials or arrangements

Definitions

• the present invention relates to a curable resin composition.
• the capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.
• Patent Document 1 discloses (A) a (meth) acrylate oligomer having a polyisoprene, polybutadiene or polyurethane as a skeleton, (B) a softening component, and (C1) phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, (Meth) selected from 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, methoxytriethylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate
• a photocurable resin composition containing an acrylate monomer is described.
• Patent Document 1 does not describe the alkoxysilane compound of the present invention.
• glass for display bodies such as LCDs has become thinner.
• the LCD is easily deformed by external stress.
• an optical functional material such as an acrylic plate or polycarbonate plate
• the difference in linear expansion between glass and acrylic or plastic molding material such as acrylic plate or polycarbonate Due to the strain at the time of molding, relaxation of molding strain and moisture absorption / drying occur in the heat resistance test and moisture resistance test, and surface accuracy changes such as dimensional change and warpage occur.
• Patent Document 2 describes a cured resin containing urethane (meth) acrylate, polybutadiene (meth) acrylate, and isoprene (meth) acrylate as components. There is no description in patent document 2 about the composition of this invention.
• Patent Document 3 As a conventional adhesive, there is a UV curable resin as in Patent Document 3. Since Patent Document 3 is a highly elastic resin based on a rigid skeletal monomer such as isobornyl (meth) acrylate, it cannot withstand the expansion and contraction of the adherend in a high temperature reliability test, causing peeling. There was a possibility.
• the present invention has found a design that can withstand the expansion and contraction of the adherend in a high-temperature reliability test by using (C) phenoxypolyethylene glycol (meth) acrylate having an EO chain. In the present invention, it is not necessary to use a monomer having a rigid skeleton such as isobornyl (meth) acrylate.
• the degree to which the adherend can be deformed in a heated atmosphere assuming the usage environment It is desirable to have the flexibility.
• Patent Document 4 contains at least one oligomer selected from the group consisting of a polyisoprene (meth) acrylate oligomer, a polybutadiene (meth) acrylate oligomer, and a polyurethane (meth) acrylate oligomer, and a hindered amine.
• oligomer selected from the group consisting of a polyisoprene (meth) acrylate oligomer, a polybutadiene (meth) acrylate oligomer, and a polyurethane (meth) acrylate oligomer, and a hindered amine.
• a photocurable adhesive composition is described. The composition of the present invention is not described in Patent Document 4.
• a photocurable dam composition along the outer periphery of a predefined area. Applying to the surface of the transparent substrate, contacting the dam composition and the photocurable fill composition, exposing the dam composition and the fill composition to actinic radiation, photocuring, and light Providing a cured adhesive, whereby the photocured fill composition and the dam composition are bonded to a transparent substrate, resulting in a display bonded to the transparent substrate.
• the boundary between the dam composition and the fill composition greatly affects the optical characteristics of the display.
• Patent document 5 is mentioned as a method of performing the said process.
• Patent Document 5 discloses a step of applying a photocurable dam composition to the surface of a transparent substrate along the outer periphery of the predetermined region in an application for bonding a liquid crystal display, and the dam composition and the photocurable property.
• a method comprising contacting a fill composition; and exposing the dam composition and the fill composition to actinic radiation to photo-cure to provide a photo-cured adhesive.
• the present invention provides, for example, sufficient adhesion when a decorative plate or icon sheet used for a display body such as a touch panel is bonded, when a transparent substrate and a transparent substrate are bonded, or when a printed part is bonded.
• the problem of the prior art that it is difficult to impart the properties, the problem of the prior art that the display surface and the optical functional material are bonded, the adhesive surface is peeled off, or the glass of the display is broken, heat resistance,
• a curable resin composition that solves the problems of the prior art, such as discoloration and strength reduction after a moisture resistance test, and the problems of the prior art of reduced display optical characteristics when the curable resin composition is used as a dam composition and a fill composition. I will provide a.
• the present invention provides a curable resin composition used when, for example, a decorative plate or an icon sheet used for a display body such as a touch panel is bonded.
• the present invention provides, for example, a curable resin composition that solves the problem of the prior art that a portion that is not directly exposed to light such as ultraviolet rays (for example, a printed ground portion) cannot be cured.
• the present invention provides a curable resin composition for bonding a decorative board or icon sheet used for a display body such as a touch panel, for bonding a transparent substrate and a transparent substrate, or for bonding a printed portion.
• a curable resin composition that also serves as a dam agent for the purpose of preventing protrusion.
• the present invention provides a curable resin composition having an effect that a boundary between a dam agent and a filling agent filling the surface is not visible. By eliminating the boundary between the dam agent and the fill agent, it is possible to suppress the optical unevenness of the display body.
• a curable resin composition containing the following (A) to (F).
• A 100 parts by mass of a polymer having a (meth) acryloyl group and having a diene-based or hydrogenated diene-based skeleton (B) having no (meth) acryloyl group, and a diene-based or 30 to 600 parts by mass of a polymer having a hydrogenated diene-based skeleton (C) (meth) acrylate having an aromatic ring (D) photopolymerization initiator (E) antioxidant (F) general formula
• a preferable aspect is as follows.
• the diene-based or hydrogenated diene-based skeleton of the component (A) is one or more skeletons selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene.
• the curable resin composition is one or more skeletons selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene.
• the curable resin composition is (4) The curable resin composition having a molecular weight of component (A) of 500 to 70000.
• the curable resin composition wherein the molecular weight of the component (B) is 500 to 70000.
• the curable resin composition, wherein the component (E) is a phenol / sulfur antioxidant.
• the curable resin composition, wherein the component (E) is an antioxidant having a phenol group and sulfur in the same molecule.
• component (G) (meth) acrylate having a hydroxyl group in the molecule, (meth) acrylate having a carboxyl group, (meth) acrylate having a nitrogen atom in the molecule, (meth) acrylic acid, and
• the curable resin composition comprising one or more compounds selected from the group consisting of (meth) acrylic acid derivatives having a nitrogen atom in the molecule.
• the 400 nm transmittance difference between the dam agent and the fill agent is 5% or less
• the refractive index difference is 0.01% or less
• the Haze difference is 0.2. % Of the curable resin composition.
• the curable resin composition capable of curing a light non-transmissive portion having a width of 1 mm or more by irradiation with ultraviolet rays of 1000 mJ / cm 2 or more.
• the curable resin composition having a cure shrinkage of 2.0% or less.
• An adhesive composition comprising the curable resin composition.
• a cured product of the adhesive composition is provided.
• the adherend is at least one selected from the group consisting of triacetylcellulose, fluorine-based polymer, polyester, polycarbonate, polyolefin, glass, and metal.
• a touch panel laminate in which an adherend is bonded with the adhesive composition is bonded with the adhesive composition.
• a liquid crystal panel laminate in which adherends are bonded together using the adhesive composition is (19) A display using the touch panel laminate. (20) A display using the liquid crystal panel laminate.
• the present invention can provide, for example, a curable resin composition that is small in coloration or discoloration due to heat and a decrease in strength after a moisture resistance test.
• One embodiment of the present invention is a novel curable resin composition.
• This curable resin composition contains, for example, components (A) to (F) described below.
• the component (A) is a polymer having a (meth) acryloyl group and a diene-based or hydrogenated diene-based skeleton.
• the main chain skeleton of the polymer is a diene-based or hydrogenated diene-based skeleton.
• the diene-based or hydrogenated diene-based skeleton is preferably at least one skeleton selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene.
• at least one selected from the group consisting of polybutadiene and polyisoprene is preferable, and polyisoprene is more preferable in terms of high adhesion durability.
• the polymer preferably has one or more (meth) acryloyl groups at the terminal or side chain of the main chain skeleton.
• those having (meth) acryloyl groups at both ends of the main chain skeleton are preferable.
• the molecular weight of the polymer is preferably 500 to 70000, more preferably 1000 to 60000, and most preferably 1000 to 55000. If the molecular weight is within this range, the cured product of the present invention has a high hardness, so that it is easy to form an adhesive layer, and the viscosity of the curable resin composition is small, so in workability and practical use in mixing in the manufacturing process. Workability is improved.
• the molecular weight of the polymer may be, for example, 500, 1000, 2000, 3000, 5000, 10000, 20000, 30000, 40000, 50000, 55000, 60000, or 70000, and any two values thereof. It may be within the range.
• the molecular weight refers to a number average molecular weight calculated as an average molecular weight per molecule.
• the number average molecular weight of polystyrene conversion measured by GPC was used.
• the average molecular weight was determined by preparing a calibration curve with commercially available standard polystyrene using GPC system (SC-8010 manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent under the following conditions. .
• an esterified polymer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate (see the following formula (1) for the structure, “UC-” manufactured by Kuraray Co., Ltd.) 203 ", manufactured by Nippon Soda Co., Ltd.,” TEAI-1000 "(terminally acrylic-modified hydrogenated 1,2-polybutadiene polymer), manufactured by Nippon Soda Co., Ltd.,” TE-2000 “(terminal acrylic modified 1,2-polybutadiene polymer) Thing) etc. are mentioned.
• an esterification polymer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate is preferable.
• the component (B) is a polymer having no (meth) acryloyl group and having a diene-based or hydrogenated diene-based skeleton.
• the main chain skeleton of the polymer is a diene-based or hydrogenated diene-based skeleton.
• the diene-based or hydrogenated diene-based skeleton is preferably at least one skeleton selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene.
• at least one selected from the group consisting of polybutadiene and polyisoprene is preferable, and polybutadiene is more preferable in terms of high adhesion durability.
• the molecular weight of the polymer is preferably 500 to 70000, more preferably 1000 to 60000, and most preferably 1000 to 55000. If the molecular weight is within this range, the hardness of the cured body is high, so that it is easy to form an adhesive layer, and the viscosity of the curable resin composition is small, so that the workability in mixing in the manufacturing process and the workability in practical applications are high. Become good.
• the molecular weight of the polymer may be, for example, 500, 1000, 2000, 3000, 5000, 10000, 20000, 30000, 40000, 50000, 55000, 60000, or 70000, and any two values thereof. It may be within the range.
• Kuraray's “LIR-30” and “LIR-50” isoprene polymer
• Kuraray's “LBR-307” and “LBR-305” butadiene polymer
• Toyobo “Byron” manufactured amorphous polyester resin
• at least one selected from the group consisting of isoprene polymer, 1,2-polybutadiene polymer, and 1,4-polybutadiene polymer is preferable, and 1,2-polybutadiene polymer and 1,4-polybutadiene are preferable.
• One or more selected from the group consisting of polymers is more preferred.
• the amount of the component (B) used is such that the adhesiveness to the adherend of the curable resin composition is particularly high and the curability is good, with respect to 100 parts by mass of the component (A). 30 to 600 parts by mass is preferable, 40 to 500 parts by mass is more preferable, and 50 to 450 parts by mass is most preferable.
• the amount of component (B) used may be 401 parts by mass or more. The amount used may be, for example, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, or 600. , Any two of them may be within the range of values.
• the component (C) is a (meth) acrylate having an aromatic ring.
• the aromatic ring may have a substituent such as an alkyl group such as a nonyl group.
• a phenoxypolyalkylene glycol (meth) acrylate having an alkylene oxide chain — (RO) n— (R is an alkylene group) is preferable, and an EO (ethylene oxide) chain — (CH 2 CH 2 O) n Phenoxypolyethylene glycol (meth) acrylate having — is more preferable.
• n is preferably 4 or more.
• nonylphenoxypolyethylene glycol (meth) acrylate is preferable.
• the amount of the component (C) used is such that the adhesion to the adherend of the curable resin composition is particularly high and the curability is good, with respect to 100 parts by mass of the component (A). It is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, and most preferably 25 to 120 parts by mass.
• the amount of component (C) used may be 101 parts by mass or more.
• the amount used may be, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, or 300. It may be within a range of two values.
• the component (D) is a photopolymerization initiator.
• D As a component, 1 or more types in the group which consists of an alkylphenone type photoinitiator and an acyl phosphine oxide type photoinitiator is preferable.
• Alkylphenone photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1- ON, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy- 2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one and the like.
• acylphosphine oxide photoinitiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. One or more of these can be used.
• the amount of component (D) used is such that the adhesion of the curable resin composition to the adherend is particularly high and the curability is good, so that component (A), component (B) and (
• the total amount of component C) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and most preferably 0.5 to 10 parts by mass with respect to 100 parts by mass in total.
• this usage-amount may be 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 20, 30, 40, or 50, for example. It may be within the range of values.
• a component is antioxidant.
• a phenol / sulfur antioxidant is preferable.
• a phenolic / sulfur antioxidant is an antioxidant having a phenol group and sulfur.
• examples of the phenol / sulfur antioxidant include an antioxidant having a phenol group and sulfur in the same molecule.
• Examples of the phenol-based / sulfur-based antioxidant include those in which an antioxidant having a phenol group and an antioxidant having sulfur are used in combination.
• sulfur sulfide is preferable.
• Antioxidants having a phenol group and sulfur in the same molecule include 4,6-bis (octylthiomethyl) -O-cresol, 4,6-bis (dodecylthiomethyl) -O-cresol, 4,6- Bis (alkylthiomethyl) -O-cresol, 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, dioctadecyl 3, 3'-thiodipropionate, didodecyl 3,3'-thiodipropionate and the like.
• the phenolic antioxidant is not particularly limited as long as it is an antioxidant having a phenol group in the molecule, and the following formula (2) An antioxidant having the following structure is preferred.
• BHT dibutylhydroxytoluene
• pentaerythritol tetrakis [3- (3,5-di-t-butyl) are used as the phenolic antioxidant.
• the sulfur-based antioxidant is not particularly limited as long as it is an antioxidant having sulfur in the molecule, and the following formula (3) An antioxidant having the following structure is preferred.
• the mass ratio of the antioxidant having a phenol group: the antioxidant having sulfur 1 to 10:10 to 1 is preferable. ⁇ 5: 5 to 1 is more preferred, and 1: 1 is most preferred.
• skeleton having an antioxidant function examples include a skeleton having a hydrocarbon group, a skeleton having a carbonyl group, a skeleton having a ketone group, and a skeleton having an ether group. Of these, alkylpropionate groups are preferred.
• sulfur-based antioxidants examples include ditridecyl-3,3′-thiodipropionate, dilauryl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, distearyl-3,3. Examples include '-thiodipropionate and dioctyl-3,3'-thiodipropionate.
• the amount of component (E) used is the sum of component (A), component (B) and component (C) in that the color and discoloration of the curable resin composition due to heat is small and the decrease in strength after the moisture resistance test is small.
• the amount is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 20 parts by mass, and most preferably 0.1 to 10 parts by mass with respect to 100 parts by mass.
• this usage-amount may be 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, 20, or 30, for example. It may be within the range.
• the component (F) is an alkoxysilane compound represented by the general formula (1).
• Formula (1) (RO) n Si [(CH 2) m CH 3] 4-n
• R is CH 2 or C 2 H 5
• n 2 to 3
• m 0 to 12.
• alkoxysilane compound of component (F) methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, etc. Is mentioned.
• one or more members selected from the group consisting of hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, and decyltriethoxysilane are preferable.
• the component (F) is different from, for example, a silane coupling agent known to improve adhesion to a substrate or the like.
• the component (F) in one embodiment of the present invention has an effect that does not affect the optical characteristics of the display when, for example, a decorative board or an icon sheet used for a display body such as a touch panel is attached.
• Component (F) is preferably used in an amount of 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on a total of 100 parts by weight of components (A), (B) and (C). More preferred is 1 to 10 parts by mass.
• this usage-amount may be 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 20, or 30, for example, and is in the range of any two of these. It may be.
• the curable resin composition of one Embodiment of this invention has (meth) acrylate which has a hydroxyl group in a molecule
• the adhesion to the adherend can be improved.
• the component (G) is a (meth) acrylate
• the (meth) acrylate is preferably a (meth) acrylate other than the component (A) or the component (C).
• the (meth) acrylate having a hydroxyl group as the component (G) is not particularly limited as long as it has a hydroxyl group in the molecule.
• the (meth) acrylate having a carboxyl group (G) is not particularly limited as long as it has a carboxyl group in the molecule.
• Examples of the (meth) acrylate having a nitrogen atom in the molecule of the component (G) include imide (meth) acrylate, amino (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, dimethylaminoethyl (meth) ) Acrylate, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, and hydroxyethyl (meth) acrylamide.
• imide (meth) acrylate amino (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, dimethylaminoethyl (meth) ) Acrylate, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, and hydroxyethyl (meth) acrylamide.
• Component (G) is 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl in terms of improving adhesion to the adherend.
• One or more compounds selected from the group consisting of (meth) acrylate, (meth) acrylic acid, and (meth) acryloylmorpholine are more preferable.
• Component (G) is preferably used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total of components (A), (B) and (C). More preferred.
• the amount used may be, for example, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, or 20, and is within the range of any two of them. May be.
• the curable resin composition of one embodiment of the present invention contains the components (A) to (F) and, if necessary, the component (G). 0% or less. Curing shrinkage is calculated by the volume specific gravity method. Due to the small curing shrinkage rate, for example, when a decorative board or icon sheet used for a display body such as a touch panel is attached, it is possible to suppress peeling due to external factors such as stress, heat, and humidity.
• the curable resin composition of one embodiment of the present invention contains the components (A) to (F) and, if necessary, the component (G), thereby containing the curable resin composition.
• the 400 nm transmittance difference between the dam composition and the fill composition is 5% or less
• the refractive index difference is 0.01% or less
• the Haze difference is 0.2% or less.
• the curable resin composition of one embodiment of the present invention contains the components (A) to (F) and, if necessary, also contains the component (G), and is cured with light or ultraviolet rays. Is possible.
• the curable resin composition of one embodiment of the present invention contains the components (A) to (F) and, if necessary, a component (G), for example, a display body such as a touch panel.
• a decorative board and an icon sheet used in the above are pasted together, particularly a portion (such as a printed ground portion) that is not directly exposed to light such as ultraviolet rays can be cured.
• the curable resin composition of one embodiment of the present invention can harden a printed base portion with a width of 1 mm or more, for example, with ultraviolet rays of 1000 mJ / cm 2 or more.
• the curable resin composition of one embodiment of the present invention is (meta) other than (A) component, (C) component, and (G) component, particularly for the purpose of further improving the adhesion to each adherend.
• Acrylates can be included.
• elastomers various paraffins, plasticizers, fillers, colorants, rust inhibitors and the like can be used as desired.
• the curable resin composition of one embodiment of the present invention can be used as an adhesive composition.
• a composite can be produced by bonding or covering an adherend with a cured body of an adhesive composition.
• the various materials of the adherend are preferably at least one selected from the group consisting of polyesters such as triacetyl cellulose, fluoropolymers, polyethylene terephthalate, polycarbonates, polyolefins such as cycloolefin polymers, glass, and metals. And at least one selected from the group consisting of glass is more preferred.
• the present invention is used for the purpose of preventing the adhesive composition from sticking out.
• the curable resin composition of one embodiment of the invention can also serve as a dam agent.
• the curable resin composition of one embodiment of the present invention can also serve as a filling agent that fills the adherend surface.
• the curable resin composition of one embodiment of the present invention can be used as a dam agent and a fill agent.
• the 400 nm transmittance difference between the dam agent and the fill agent is 5% or less
• the refractive index difference is 0.01 or less
• the Haze difference is 0.2% or less. Therefore, the boundary line can be eliminated.
• the adherend adhered with the curable resin composition of one embodiment of the present invention can be reworked (reused) after being completely cured.
• the rework method is not particularly limited, but the adherends are disassembled by applying a load of 0.01 to 100 N between the one or two kinds of adherends bonded together, and the adherend after disassembly
• the body can be reused.
• polymerized product includes a compound having a monomer unit.
• the degree of polymerization of the polymer may be, for example, 2, 10, 100, 200, 300, or 400 or more, and may be in the range of any two values thereof.
• “or” is used when “at least one or more” of the items listed in the text can be adopted.
• the range includes the two values themselves.
• “A to B” means A or more and B or less.
• a polymer having a (meth) acryloyl group and having a diene-based or hydrogenated diene-based skeleton the following compounds were selected.
• Y is an ethylene group
• R is a methyl group
• (A-3) Isoprene polymer (“UC-102” manufactured by Kuraray Co., Ltd.) (Number average molecular weight 2000
• B-1 Isoprene polymer (“LIR-30” manufactured by Kuraray Co., Ltd.) (number average molecular weight 28000 in terms of polystyrene by GPC)
• the following compounds were selected as the phenoxy polyethylene glycol (meth) acrylate of component (C).
• G-1 Methacrylic acid (“MAA” manufactured by Mitsubishi Rayon Co., Ltd.)
• G-2) Acryloyl morpholine (“ACMO” manufactured by Kojin Co., Ltd.)
• G-3) 2-hydroxyethyl methacrylate manufactured by Kyoeisha Chemical Co., Ltd., “light ester“ HO-250 ”, abbreviated as 2-HEMA
• PET Polyethylene terephthalate
• Peel adhesion strength between polyethylene terephthalate test pieces Test pieces (width 50 mm ⁇ length 10 mm ⁇ thickness 0.05 mm) of biaxially stretched PET films (Lumirror T60, average thickness 190 ⁇ m, manufactured by Toray Industries, Inc.) are used as the adhesive composition. Then, the adhesive layer was bonded with a thickness of 30 ⁇ m and an adhesive area of 40 mm long ⁇ 10 mm wide.
• the bond strength was measured.
• the light irradiation conditions followed the method described in [Photocurability].
• the peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.
• the tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
• the peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.
• the bond strength was measured.
• the light irradiation conditions followed the method described in [Photocurability].
• the peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.
• Pvdf Polyvinylidene fluoride film (average thickness 40 ⁇ m, “DX film” manufactured by Denki Kagaku Kogyo Co., Ltd.) test pieces (width 50 mm ⁇ length 10 mm ⁇ thickness 0.04 mm) are bonded to each other with a curable resin composition as an adhesive.
• the adhesive layer was bonded with a thickness of 10 ⁇ m and an adhesive area of 40 mm long ⁇ 10 mm wide.
• the initial 180 ° peel strength was measured by pulling the two film ends that were not in close contact with the test piece that was adhered with the adhesive composition, thereby peeling the portions where the films were in close contact with each other. .
• After curing by light irradiation by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed.
• the bond strength was measured.
• the light irradiation conditions followed the method described in [Photocurability].
• the peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.
• the tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
• the specific gravity bottle was filled with the curable resin composition, the mass in the air and the mass in pure water were measured, and the liquid specific gravity was calculated. Furthermore, the curable resin composition is cured by the method described in [Photocurability] to produce a cured product having a width of 25 mm ⁇ length of 25 mm ⁇ thickness of 2 mm, and the mass in the air and the mass in pure water are measured. It measured and computed hardened
• cured material specific gravity. The cure shrinkage was calculated from the ratio of liquid specific gravity and cured product specific gravity. Curing shrinkage ((cured product specific gravity ⁇ liquid specific gravity) / cured product specific gravity) ⁇ 100 (%)
• Tempax (registered trademark) glass (width 25 mm ⁇ length 25 mm ⁇ thickness 2 mm), curable resin composition as adhesive composition, adhesive layer thickness 100 ⁇ m, adhesive area 1.0 mm 2 Glued and cured.
• the light irradiation conditions followed the method described in [Photocurability].
• the test piece bonded with the adhesive composition was exposed to an environment of 85 ° C. and 85% relative humidity for 1000 hours using a constant temperature and humidity chamber. After the exposure, the ⁇ b value of the test piece adhered with the adhesive composition was measured with a color measuring device (“UV-VISABLE SPECTROPOHOTOMETER” manufactured by SHIMADZU) to determine the yellowing degree.
• UV-VISABLE SPECTROPOHOTOMETER manufactured by SHIMADZU
• the test piece bonded with the adhesive composition was used in an instant multi-side light system (“instant multi-side light system” manufactured by Otsuka Electronics Co., Ltd.) in two thickness directions (50 ⁇ m position of the adhesive composition, The transmittance at 400 nm at a position of 150 ⁇ m was measured. The difference between the transmittances at the two points was defined as the transmittance difference.
• the test piece bonded with the adhesive composition was used (the “KPR-2000” manufactured by Shimadzu Device Manufacturing Co., Ltd.), and the refractive index in two thickness directions (50 ⁇ m position and 150 ⁇ m position of the adhesive composition). was measured. The difference in refractive index between the two points was taken as the refractive index difference.
• a curable resin composition in which coloring and discoloration due to heat and reduction in strength after a moisture resistance test are reduced while maintaining flexibility. Moreover, if the curable resin composition of a present Example is used, the optical display body or touch sensor bonded together using the curable resin composition will be obtained.
• the curable resin composition of this example can be used as a dam agent or a fill agent. At this time, since the transmittance difference, refractive index difference, and Haze difference between the dam composition and the fill composition are small, the optical characteristics of the display are not affected.
• the curable resin composition of this example may not use a monomer having a rigid skeleton such as isobornyl (meth) acrylate.
• the present invention can provide, for example, a curable resin composition that retains flexibility while eliminating coloration or discoloration due to heat and a decrease in strength after a moisture resistance test.
• a curable resin composition that retains flexibility while eliminating coloration or discoloration due to heat and a decrease in strength after a moisture resistance test.
• the transmittance difference, refractive index difference, and Haze difference between the dam composition and the fill composition are reduced, it is difficult to see the boundary line between the dam agent and the fill agent, and at the boundary between the dam agent and the fill agent. There is little distortion in the image of the display device.
• the curable resin composition of the present invention can be used for an adhesive composition for a touch panel laminate or a liquid crystal panel laminate.
• the touch panel laminate and the liquid crystal panel laminate of the present invention can be used as a display.
• the curable resin composition of the present invention can improve curability even when a transparent portion is bonded.

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• 2014
  • 2014-04-09 WO PCT/JP2014/060269 patent/WO2014168173A1/ja active Application Filing
  • 2014-04-09 JP JP2015511281A patent/JP6454268B2/ja active Active
  • 2014-04-09 TW TW103113013A patent/TW201446915A/zh unknown

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