WO2015111584A1 - Composition de résine durcissable et corps stratifié et dispositif d'affichage d'images utilisant la composition de résine durcissable - Google Patents

Composition de résine durcissable et corps stratifié et dispositif d'affichage d'images utilisant la composition de résine durcissable Download PDF

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WO2015111584A1
WO2015111584A1 PCT/JP2015/051413 JP2015051413W WO2015111584A1 WO 2015111584 A1 WO2015111584 A1 WO 2015111584A1 JP 2015051413 W JP2015051413 W JP 2015051413W WO 2015111584 A1 WO2015111584 A1 WO 2015111584A1
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resin composition
curable
curable resin
meth
monomer
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PCT/JP2015/051413
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English (en)
Japanese (ja)
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牧人 中村
明暢 中原
薫 小黒
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旭硝子株式会社
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Priority to JP2015559072A priority Critical patent/JP6443347B2/ja
Publication of WO2015111584A1 publication Critical patent/WO2015111584A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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

Definitions

  • the present invention relates to a curable resin composition, and a laminate and an image display device using the curable resin composition.
  • an image display device an image display device in which a touch panel and a protective plate are laminated on a display device such as a liquid crystal display device via a transparent resin layer as an adhesive layer is known. Also known are transparent panels, laminated glass, etc., in which a transparent resin layer is sandwiched between a pair of substrates. For forming the transparent resin layer, a method of applying and curing a curable resin composition is widely used.
  • Such a curable resin composition is required to have an appropriate viscosity and excellent applicability.
  • the formed transparent resin layer is required to have an appropriate elastic modulus, adhesiveness, heat resistance, and the like that can satisfactorily adhere an object, and also has a low dielectric constant.
  • the transparent resin layer has been made thinner, and the demand for lowering the dielectric constant has increased.
  • the transparent resin layer is also required to have characteristics such as moisture and heat resistance that do not cause white turbidity due to moisture even under high temperature and high humidity conditions.
  • a curable resin composition for forming a transparent resin layer for example, a composition containing polypropylene glycol urethane acrylate and a curable monomer having a hydroxyl group such as 2-hydroxybutyl methacrylate is known (Patent Document). See 1 and 2.).
  • the transparent resin layer formed from the curable resin composition containing a curable monomer having a hydroxyl group has hydrophilicity based on the curable monomer having a hydroxyl group, and thus can suppress aggregation of moisture causing white turbidity, Excellent moisture and heat resistance.
  • cured products formed from the curable resin compositions described in Patent Documents 1 and 2 are excellent in moist heat resistance but have a high dielectric constant.
  • An object of the present invention is to provide a curable resin composition capable of forming a cured product having a low dielectric constant and excellent moisture and heat resistance, and a laminate and an image display device using the curable resin composition.
  • the present invention provides a curable resin composition having the following configurations [1] to [12], and a laminate and an image display device using the curable resin composition.
  • a curable resin composition containing the following curable oligomer (A), the following curable monomer (B), and a rosin ester (D), and optionally further containing the following curable monomer (C). Because The ratio of the curable oligomer (A) in the curable resin composition is 5 to 50% by mass, the ratio of the curable monomer (B) is 4 to 15% by mass, and the ratio of the curable monomer (C) is A curable resin composition, wherein 0 to 30% by mass and the ratio of the rosin ester (D) is 5 to 30% by mass.
  • Curable monomer (B) A tertiary amine compound having a (meth) acryloyl group.
  • the ratio of the curable monomer (B) in the total 100 mass% of the curable oligomer (A), the curable monomer (B), and the curable monomer (C) is 7 to 20 mass. % Of the curable resin composition according to [1].
  • the curable resin composition contains the curable monomer (C), and the ratio of the curable monomer (C) in the curable resin composition is 5 to 25% by mass.
  • the curable monomer (B) is at least selected from the group consisting of (meth) acryloylmorpholine, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and N- (meth) acryloyloxyethylhexahydrophthalimide.
  • a display device [11] a display device; A transparent substrate disposed opposite to the viewing surface side of the display device; A cured resin layer sandwiched between the display device and the transparent substrate; A laminate having The laminate is a laminate in which the cured resin layer is a cured resin layer obtained by curing the curable resin composition of any one of [1] to [10].
  • An image display device having a cured resin layer obtained by curing the curable resin composition according to any one of [1] to [10].
  • curable resin composition capable of forming a cured product having a low dielectric constant and excellent heat and heat resistance, and a laminate and an image display device using the curable resin composition.
  • CH 2 C (R 10 ) C (O) - group represented by (wherein, R 10 represents a hydrogen atom or a methyl group.)
  • R 10 represents a hydrogen atom or a methyl group.
  • the (meth) acryloyl group is a general term for an acryloyl group and a methacryloyl group.
  • a group represented by CH 2 ⁇ C (R 10 ) C (O) O— is referred to as a (meth) acryloyloxy group.
  • a compound represented by CH 2 ⁇ C (R 10 ) C (O) OH is referred to as (meth) acrylic acid.
  • an ester of (meth) acrylic acid is referred to as (meth) acrylate.
  • a compound represented by CH 2 ⁇ C (R 10 ) C (O) NH 2 is referred to as (meth) acrylamide.
  • (meth) acryloyl” and the like are also used in specific compound names.
  • the unit represented by the formula (I) is referred to as a unit (I), and the same applies to units represented by other formulas.
  • the index when the polyol and the polyisocyanate are reacted is a value obtained by multiplying the ratio obtained by dividing the number of equivalents of the isocyanate group of the polyisocyanate by the number of equivalents of the hydroxyl group of the polyol by 100.
  • “transparent” means a state in which the other surface side can be visually recognized from one surface side in the whole or a part of the cured product or substrate of the curable resin composition. Even when the visible light transmittance is low due to absorption, reflection, or optical phase change of a part of the light incident on the cured product or the substrate, the state where the other surface side can be seen from one surface side is “transparent” "include.
  • the curable resin composition of the present invention contains the following curable oligomer (A), the following curable monomer (B), and a rosin ester (D), and optionally further contains the following curable monomer (C). contains.
  • Oligomer (A2) obtained by reacting Curable monomer (B): A tertiary amine compound having a (meth) acryloyl group.
  • Curable oligomer (A) (hereinafter also referred to as “oligomer (A)”), curable monomer (B) (hereinafter also referred to as “monomer (B)”) and curable monomer (C) (hereinafter referred to as “ Monomer (C) ”) has a (meth) acryloyl group as a curable group and has curability based thereon.
  • the curable resin composition of the present invention can be suitably used for forming a cured resin layer in a laminate having a pair of substrates and a cured resin layer sandwiched between the pair of substrates.
  • a laminate as will be described in detail later, for example, a display device and a transparent substrate made of a glass plate, a transparent resin plate, and the like disposed opposite to the viewing surface side of the display device, and the pair of substrates described above
  • the laminated body considered is mentioned.
  • the transparent laminated body which has a pair of transparent substrate which consists of a glass plate, a transparent resin board, etc. is mentioned.
  • the curable resin composition of the present invention further includes a cured resin layer in an image display device in which a transparent substrate such as a touch panel or a protective plate is laminated on a display device such as a liquid crystal display device via a cured resin layer. It can be used suitably for formation.
  • the oligomer (A) is obtained by reacting a polydiene polyol (a1) with a polyisocyanate (a2) at a ratio that causes an index to exceed 100.
  • An oligomer (A1) obtained by reacting a curable monomer (a3) having an acryloyl group, or Curable monomer (a4) having an isocyanate group and a (meth) acryloyl group on a hydroxyl group-terminated prepolymer obtained by reacting polydiene polyol (a1) and polyisocyanate (a2) at a ratio of 100 or less.
  • the oligomer (A) When the oligomer (A) is used, a cured product having a low dielectric constant and excellent heat resistance and strength is easily obtained. In addition, it is preferable that the dielectric constant in 10kHz of hardened
  • the polydiene polyol (a1) is a compound having at least one of a polybutadiene chain and a polyisoprene chain and a number average molecular weight of 500 to 10,000 having two or less hydroxyl groups.
  • the polybutadiene chain has a unit derived from butadiene (hereinafter also referred to as “butadiene unit”), and the polyisoprene chain has a unit derived from isoprene (hereinafter also referred to as “isoprene unit”).
  • the butadiene unit constituting the polybutadiene chain may be a hydrogenated double bond
  • the isoprene unit constituting the polyisoprene chain may be a hydrogenated double bond
  • the polybutadiene chain may have units other than butadiene units
  • the polyisoprene chain may have units other than isoprene units.
  • Polydiene polyol (a1) may be used individually by 1 type, or may use 2 or more types together.
  • the number of hydroxyl groups per molecule of the polydiene polyol (a1) is more than 1 and not more than 2 as an average value.
  • the number of hydroxyl groups is preferably 1.5 to 2 as an average value.
  • the hydroxyl value (OHV) of the polydiene polyol (a1) is preferably 11 to 224 mgKOH / g, more preferably 22 to 112 mgKOH / g.
  • the hydroxyl value can be measured by the method described in JISK1557-1 (2007 edition).
  • the value of the storage elastic modulus is 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa
  • the cured product and the object can be favorably bonded, and the cured product is provided as an adhesive layer. It is possible to prevent the laminated body from warping.
  • a cured resin layer made of the cured product is provided between a display device and a transparent substrate such as a protective plate disposed opposite to the viewing surface side of the display device, occurrence of color unevenness is also prevented. it can.
  • the number average molecular weight in terms of polystyrene by GPC of the polydiene polyol (a1) is 500 to 10,000, more preferably 1,000 to 5,000, and particularly preferably 1,500 to 4,000.
  • the molecular weight of the polydiene polyol (a1) is within the above range, the curable resin composition has a low viscosity, and the cured product has excellent flexibility. Therefore, the cured resin layer made of the cured product is suitable as an adhesive layer.
  • it can be suitably used as an adhesive layer when laminating a transparent substrate such as a protective plate, a touch panel or the like.
  • the skeleton has a unit composed of at least one of the unit represented by the following formula (I) and the unit represented by the following formula (II). And a compound (a11) having a hydroxyl group at one or both ends of the molecule.
  • Unit (I) is a unit with 1,4 bonds
  • unit (II) is a unit with 1,2 bonds. There is no restriction
  • the polydiene polyols (a1) as the compound having a polyisoprene chain, a unit composed of at least one of a unit represented by the following formula (IV) and a unit represented by the following formula (V) is used as a skeleton. And a compound (a12) having a hydroxyl group at one or both ends of the molecule.
  • the unit (IV) is a unit with 1,4 bonds
  • the unit (V) is a unit with 1,2 bonds.
  • the solid and dotted double lines indicate single bonds or double bonds.
  • the single bond is a hydrogenated double bond.
  • Compound (a11) can be produced, for example, by a method in which butadiene is polymerized to obtain a polymer, hydrogenated as necessary, and then a hydroxyl group is introduced at the end of the polymer molecule.
  • Methods for polymerizing butadiene include ( ⁇ ) a method in which butadiene is polymerized in a solution using a Ziegler catalyst, a lithium catalyst or a radical polymerization initiator, and ( ⁇ ) a method in which butadiene is polymerized in the presence of a sodium catalyst in the solution. Can be mentioned.
  • a polymer in which butadiene is mainly polymerized with 1,4 bonds can be obtained.
  • butadiene is mainly polymerized with 1,2 bonds.
  • a polymer can be obtained.
  • Compound (a12) can be produced by, for example, a method of polymerizing isoprene to obtain a polymer, hydrogenating as necessary, and then introducing a hydroxyl group into the terminal of the polymer molecule.
  • a method for polymerizing isoprene isoprene may be used in place of butadiene in the methods ( ⁇ ) and ( ⁇ ).
  • Examples of the method of introducing a hydroxyl group at the polymer molecule end include a method of adding an epoxy compound to a reaction solution containing a polymer obtained by polymerizing butadiene or isoprene.
  • Examples of the epoxy compound include ethylene oxide and propylene oxide.
  • the compound (a11) may have a unit (u1) other than the unit (I) and the unit (II), and the compound (a12) is a unit other than the unit (IV) and the unit (V) ( u1) may be included.
  • Examples of the monomer (m1) forming the unit (u1) include the following monovinyl monomers. ⁇ -olefins such as ethylene, propylene, butene-1, pentene-1,2-methylpentene-1, hexene-1,3-methylhexene-1, cyclohexene; styrene, 4-methylstyrene, ⁇ -methylstyrene, etc.
  • Styrene-based monomers ethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dimethylaminoethyl acrylate
  • Ethylenically unsaturated carboxylic acid esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, acrylamide, Me Unsaturated monoolefins such as ethylene, propylene and butylene; vinyl halide monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; vinyl esters such as vinyl acetate and
  • the amount of the monomer (m1) used is 100 parts by mass or less with respect to 100 parts by mass of butadiene and isoprene used in the polymerization reaction of butadiene and isoprene. It is preferably 50 parts by mass or less, more preferably 10 parts by mass or less.
  • Non-yellowing polyisocyanate As the polyisocyanate (a2), non-yellowing polyisocyanate is preferable, and non-yellowing diisocyanate having two isocyanate groups is more preferable.
  • the non-yellowing type polyisocyanate means a polyisocyanate compound having no isocyanate group directly bonded to the carbon atom constituting the aromatic nucleus. Examples of the non-yellowing polyisocyanate include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates that do not have an isocyanate group directly bonded to a carbon atom constituting an aromatic nucleus, and the like.
  • aliphatic diisocyanates such as trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, 1,2-cyclopropanediyl diisocyanate, 1,3-cyclobutanediyl diisocyanate, 1,4-cyclohexanediyl diisocyanate, 1,3- Examples thereof include cycloaliphatic diisocyanate, isophorone diisocyanate, 4-methyl-cyclohexane-1,3-diyl-diisocyanate, alicyclic diisocyanate such as dicyclohexylmethane diisocyanate, and norbornane diisocyanate, and non-yellowing aromatic diisocyanate such as xylene diisocyanate.
  • the prepolymer modified body of these diisocyanates a nurate modified body, a urea modified body, a carbodiimide modified body, etc. are mentioned.
  • hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylene diisocyanate, norbornane diisocyanate, trimethylhexamethylene diisocyanate, and prepolymer modified products thereof, nurate modified products, urea modified products, carbodiimide modified products, and the like are preferable.
  • isophorone diisocyanate and hexamethylene diisocyanate are particularly preferable.
  • Polyisocyanate (a2) may be used individually by 1 type, or may use 2 or more types together.
  • the curable monomer (a3) has a hydroxyl group and a (meth) acryloyl group.
  • the number of hydroxyl groups in one molecule is preferably one in terms of ease of control of the molecular structure of the resulting oligomer (A1), viscosity, and the like.
  • the number of (meth) acryloyl groups in one molecule is not particularly limited, but it is preferably 1 in terms of availability.
  • As the curable monomer (a3) hydroxyalkyl (meth) acrylate is preferable.
  • hydroxyalkyl group a linear or branched hydroxyalkyl group having 1 to 10 carbon atoms is preferable, and a hydroxyalkyl group having 1 to 6 carbon atoms is particularly preferable.
  • the curable monomer (a3) include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxy-n-propyl (meth) acrylate, and 2-hydroxy-n-propyl (meth) acrylate.
  • curable monomer (a3) hydroxymethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate are preferable in terms of reactivity.
  • a curable monomer (a3) may be used individually by 1 type, or may use 2 or more types together.
  • the curable monomer (a4) has an isocyanate group and a (meth) acryloyl group.
  • the number of isocyanate groups in one molecule is preferably one in terms of ease of control of the molecular structure of the resulting oligomer (A2), viscosity, and the like.
  • the number of (meth) acryloyl groups in one molecule is not particularly limited, but it is preferably 1 in terms of availability.
  • an isocyanate alkyl (meth) acrylate is preferable.
  • the alkyl part of the isocyanate alkyl preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • a curable monomer (a4) may be used individually by 1 type, or may use 2 or more types together.
  • the oligomer (A) is either the oligomer (A1) or the oligomer (A2).
  • the oligomer (A1) is an oligomer produced by the method (1) below
  • the oligomer (A2) is an oligomer produced by the method (2) below.
  • oligomers (A1) and oligomers (A2) having a constant molecular weight are easily obtained.
  • the molecular weight is constant, the reactivity of the oligomer (A1) and the oligomer (A2) can be made uniform, and the properties such as the elastic modulus of the obtained cured product can be easily controlled.
  • polydiene polyol (a1) and polyisocyanate (a2) are reacted at a ratio (an isocyanate group is excessive with respect to a hydroxyl group) at an index of more than 100.
  • the polydiene polyol (a1) and the polyisocyanate (a2) are reacted at a ratio (hydroxyl group is excessive with respect to the isocyanate group) at an index of less than 100 to give a hydroxyl group.
  • a method in which a terminal prepolymer is obtained and the curable monomer (a4) is reacted with the hydroxyl group terminal prepolymer.
  • the index when the polydiene polyol (a1) and the polyisocyanate (a2) are reacted is preferably more than 100 and 200 or less, and 105 to 190 Is more preferable, and 110 to 180 is particularly preferable. If an index is the said range, an isocyanate group terminal prepolymer will be easy to be obtained effectively.
  • the use amount of the curable monomer (a3) is preferably such that the equivalent ratio is such that the isocyanate group of the isocyanate group-terminated prepolymer: the hydroxyl group of the curable monomer (a3) is in the range of 1: 1.3 to 0.25. An amount in the range of 1: 1.1 to 0.3 is more preferable.
  • the equivalent number of hydroxyl groups of the curable monomer (a3) is less than 1 with respect to the equivalent number of isocyanate groups of the isocyanate group-terminated prepolymer, the curable monomer (a3) and the aliphatic group It is preferable to use a monohydric alcohol in combination so that an unreacted isocyanate group does not remain at the end of the oligomer (A1).
  • the number of equivalents of the isocyanate group of the isocyanate group-terminated prepolymer is equal to the number of hydroxyl groups of the curable monomer (a3) and the aliphatic monohydric alcohol.
  • the number of equivalents of isocyanate groups in the isocyanate group-terminated prepolymer is preferably equal to the number of equivalents of hydroxyl groups of the curable monomer (a3) and aliphatic monohydric alcohol. More preferably, it is used so as to be equal to the total number of equivalents of the hydroxyl groups.
  • the curable monomer (a3) and the aliphatic monohydric alcohol are reacted with the isocyanate group-terminated prepolymer, the isocyanate group-terminated prepolymer and the curable monomer (a3) are reacted first, and then the aliphatic 1
  • the aliphatic monohydric alcohol is preferably a monohydric alcohol having 2 to 12 carbon atoms.
  • the number of (meth) acryloyl groups per molecule of the oligomer (A1) is preferably 0.3 to 2 as an average value, and within this range, depending on the elastic modulus of the target cured product, It is preferable to adjust the number of (meth) acryloyl groups.
  • the number of (meth) acryloyl groups per molecule is more preferably 1.2 to 2, and particularly preferably 1.5 to 2.
  • the number of (meth) acryloyl groups can be adjusted by the combined ratio of the curable monomer (a3) and the aliphatic monohydric alcohol.
  • the index when the polydiene polyol (a1) and the polyisocyanate (a2) are reacted is preferably 50 or more and less than 100, and 51 to 95 Is more preferable, and 52 to 91 is particularly preferable.
  • the hydroxyl group-terminated prepolymer is preferred because of its low viscosity.
  • the amount of the curable monomer (a4) used is preferably such that the equivalent ratio is such that the hydroxyl group of the hydroxyl-terminated prepolymer: isocyanate group of the curable monomer (a4) is in the range of 1: 1 to 0.2. An amount in the range of 0.7 to 0.3 is more preferable.
  • the oligomer (A2) when the equivalent number of isocyanate groups of the curable monomer (a4) is less than 1 relative to the equivalent number of hydroxyl groups of the hydroxyl group-terminated prepolymer, the oligomer (A2) includes a hydroxyl group-terminated prepolymer.
  • the derived hydroxyl group remains, and the number of (meth) acryloyl groups introduced by the curable monomer (a4) decreases accordingly.
  • the obtained cured product has a low elastic modulus and excellent flexibility.
  • the number of (meth) acryloyl groups possessed by the oligomer (A2) is preferably 0.2 to 2 as an average value per molecule.
  • the number of (meth) acryloyl groups introduced according to the elastic modulus of the target cured product is more preferably 0.3 to 1.5, and particularly preferably 0.4 to 1.2.
  • the number of (meth) acryloyl groups can be adjusted by the amount of the curable monomer (a4) used.
  • the resulting oligomer (A2) may have hydroxyl groups derived from the hydroxyl group-terminated prepolymer, but since the concentration of hydroxyl groups relative to the molecular weight of the oligomer (A2) is low, the dielectric constant of the cured product comprising the curable resin composition The impact on is small.
  • a tertiary amine catalyst or a metal catalyst is preferable.
  • a catalyst comprising a carboxylic acid metal salt or an organometallic compound is preferable, and tin is preferable as the metal species.
  • tertiary amine catalyst examples include, for example, monoamines such as triethylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N Diamines such as '-tetramethylpropanediamine, N, N, N', N'-tetramethylhexanediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, N, N, N', Triamines such as N ′′, N ′′ -pentamethyldipropylenetriamine and tetramethylguanidine, triethylenediamine, N, N-dimethylpiperazine, N-methyl-N ′-(2-dimethylamino) -ethylpiperazine, N-methyl Cyclic amines such as morpholine, N- (N ′, N′-dimethylaminoethyl
  • the metal catalyst include, for example, stannous diacetate, stannous octoate, stannous dilaurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin distearate, dioctyltin dilaurate , Dibutyltin marker peptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin mercaptide, dioctyltin thiocarboxylate, tetrabutoxytitanium, tetraisopropoxytitanium, bismuth tris (2-ethylhexanoate), bismuth octylate, neodecane Examples thereof include bismuth acid lead, lead octoate, lead naphthenate, nickel naphthenate,
  • a catalyst may be used individually by 1 type, or may use 2 or more types together.
  • the amount of the catalyst used is preferably in the range of 0.01 to 3 parts by mass in the case of a tertiary amine catalyst with respect to 100 parts by mass of the polydiene polyol (a1), and 0.001 in the case of a metal catalyst.
  • the range of ⁇ 0.1 parts by mass is preferred.
  • the reaction of the polydiene polyol (a1), the polyisocyanate (a2) and the curable monomer (a3) or (a4) is carried out without solvent or in a suitable inert solvent. Usually, it is carried out in the absence of a solvent.
  • the inert solvent examples include aromatic hydrocarbons such as benzene, toluene, and xylene; ester solvents such as methyl acetate, ethyl acetate, and n-propyl acetate; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, Monomers such as styrene and propylene; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane and 1,4-dioxane Examples thereof include ether solvents; nitrile solvents such as acetonitrile and benzonitrile; dimethyl sulfoxide; phosphoric acid amide solvents such as hexamethylphosphorotriamide (HMPT) and hexamethylphosphoroamide (
  • the number average molecular weight in terms of polystyrene by GPC of the oligomer (A) is preferably 2,000 to 500,000, more preferably 2,400 to 50,000.
  • the average number of (meth) acryloyl groups per molecule of the curable oligomer (A) is preferably 0.2 to 2. Within this range, the number of (meth) acryloyl groups can be adjusted according to the elastic modulus of the target cured product.
  • the oligomer (A1) 0.3 to 2 is preferable, and in the case of the oligomer (A2), 0.2 to 2 is preferable.
  • the average number of (meth) acryloyl groups per molecule of the curable oligomer (A) is more preferably 0.4-2.
  • the proportion of the oligomer (A) in 100% by mass of the curable resin composition is 5 to 50% by mass, preferably 7 to 45% by mass, and more preferably 9 to 40% by mass. If the ratio of the oligomer (A) is less than the lower limit of the above range, the heat resistance and strength of the cured product of the curable resin composition will be insufficient. When the upper limit of the above range is exceeded, the flexibility and the viscosity of the curable resin composition are inferior.
  • Monomer (B) is a tertiary amine compound having a (meth) acryloyl group.
  • the monomer (B) has hydrophilicity based on a tertiary amino group. Therefore, in the hardened
  • the cured product has a haze of 0.5% or less after being left for 180 hours under conditions of a temperature of 65 ° C. and a relative humidity of 93%.
  • the monomer (B) tends to have a small relative dielectric constant while having hydrophilicity.
  • Monomers (B) include, for example, tertiary amino groups such as (meth) acryloylmorpholine, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and N- (meth) acryloyloxyethylhexahydrophthalimide and ( And monomers having one (meth) acryloyl group.
  • the monomer (B) is preferably a tertiary amine having a (meth) acryloyl group and a cyclic structure, and an alicyclic or saturated heterocyclic tertiary amine having a (meth) acryloyl group.
  • a monomer (B) may be used individually by 1 type, or may use 2 or more types together.
  • (meth) acryloyl morpholine is preferable at the point which can form the hardened
  • the proportion of the monomer (B) in 100% by mass of the curable resin composition is 4 to 15% by mass, preferably 4 to 8% by mass. Further, the ratio of the monomer (B) in the total 100 mass% of the oligomer (A), the monomer (B), and the monomer (C) described later is preferably 7 to 20 mass%, and 11 to 20 mass%. More preferred.
  • the proportion of the monomer (B) is less than the lower limit of the above range, the wet heat resistance of the cured product of the curable resin composition is lowered, and the adhesion of the cured product to the object is lowered.
  • compatibility with other components decreases.
  • the monomer (C) is an alkyl (meth) acrylate having an alkyl group part having 8 to 22 carbon atoms. Since the monomer (C) has an alkyl group having 8 to 22 carbon atoms, a cured product formed from the curable resin composition containing the monomer (C) has excellent flexibility.
  • the alkyl group may be linear or branched.
  • Examples of the monomer (C) include lauryl (meth) acrylate, stearyl acrylate, isostearyl acrylate, and the like.
  • a monomer (C) may be used individually by 1 type, or may use 2 or more types together.
  • lauryl (meth) acrylate is preferred because it is excellent in compatibility with other components and can form a cured product having excellent flexibility.
  • the proportion of the monomer (C) in 100% by mass of the curable resin composition is 0 to 30% by mass, preferably 5 to 25% by mass, and more preferably 10 to 20% by mass.
  • the proportion of the monomer (C) is within the above range, the flexibility of the cured product of the curable resin composition is in an appropriate range.
  • Non-curable polymer component The curable resin composition of the present invention contains a rosin ester (D). Moreover, you may contain further non-curable polymer components other than rosin ester (D). As the non-curable polymer component other than the rosin ester (D), polybutene and polybutadiene are preferable. By containing the said non-curable polymer component, the viscosity of a curable resin composition falls and the handleability of a curable resin composition is excellent. Moreover, it becomes easy to form the hardened
  • the curable resin composition of the present invention contains a rosin ester (D).
  • the rosin ester is obtained by esterifying rosin.
  • white turbidity of the curable resin composition resulting from containing the above-mentioned monomer (B) can be suppressed.
  • the compatibility is improved and the curable resin composition becomes cloudy even if the proportion of the monomer (B) in the curable resin composition is relatively large. do not do. Therefore, it becomes possible to mix
  • the rosin ester has an alicyclic skeleton having low polarity and an ester group having high polarity, and is considered to contribute to compatibilization of the oligomer (A) having low polarity and the monomer (B) having high polarity.
  • the rosin ester may be a hydrogenated rosin ester in which at least a part of the double bond is hydrogenated.
  • the rosin ester has an acid value of preferably 100 or less, and more preferably 30 or less.
  • the lower limit of the acid value is better and 0 is preferable.
  • the softening point of the rosin ester is preferably 80 to 120 ° C, more preferably 90 to 110 ° C.
  • the color tone is preferably 10 or less as the Gardner color number, and more preferably 250 or less as the Hazen color number.
  • the ratio of the rosin ester (D) in 100% by mass of the curable resin composition is 5 to 30% by mass from the viewpoint of suppressing the white turbidity of the curable resin composition to improve transparency and adjusting the refractive index of the cured product. It is preferably 10 to 25% by mass.
  • the curable resin composition of the present invention preferably contains at least one selected from polybutene and polybutadiene as the non-curable polymer component.
  • a curable resin composition containing at least one of polybutene and polybutadiene has an appropriate viscosity and is excellent in coatability.
  • the obtained cured product is excellent in flexibility, heat resistance, and hardly yellows even under high temperature conditions.
  • the polybutadiene those having a 1,4 bond amount in the range of 20 to 50% are preferable.
  • the curable resin composition containing polybutadiene having a 1,4 bond amount within the above range has an appropriate viscosity and is excellent in coating property. Moreover, the cured product of the curable resin composition is excellent in heat resistance and hardly yellows even under high temperature conditions.
  • the number average molecular weight in terms of polystyrene by GPC of polybutene and polybutadiene is preferably 300 to 4,000, more preferably 500 to 2,000.
  • a curable resin composition containing at least one of polybutene and polybutadiene having a number average molecular weight within the above range has an appropriate viscosity and is excellent in coatability. Further, the cured product of the curable resin composition is excellent in flexibility, excellent in heat resistance, and hardly yellowed under high temperature conditions.
  • the total proportion of polybutene and polybutadiene in 100% by mass of the curable resin composition is preferably 5 to 55% by mass, and preferably 15 to 45% by mass from the viewpoints of the applicability of the curable resin composition and the heat resistance of the cured product. % Is more preferable.
  • the curable resin composition of the present invention preferably contains a photopolymerization initiator. That is, the curable resin composition of the present invention is preferably a photocurable resin composition in which a curing reaction proceeds by light irradiation.
  • the photopolymerization initiator one that is excited by irradiation with visible light or ultraviolet light (wavelength 300 to 400 nm) and activated to accelerate the curing reaction is preferable. Specific examples include benzoin ether photopolymerization initiators, ⁇ -hydroxyalkylphenone photopolymerization initiators, and acylphosphine oxide photopolymerization initiators.
  • the photopolymerization initiator examples include benzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, acetophenone, 3-methylacetophenone, benzoyl, benzoin isobutyl ether, benzoin isopropyl ether, Benzoin ethyl ether, anthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2 -Methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.
  • 1-hydroxycyclohexyl phenyl ketone 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethyl) Acylphosphine oxide photopolymerization initiators such as benzoyl) -phenylphosphine oxide are preferred.
  • 1-hydroxycyclohexyl phenyl ketone and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide are particularly preferred from the viewpoint that the curable resin composition can be sufficiently cured with a small amount of addition.
  • a photoinitiator may be used individually by 1 type, or may use 2 or more types together.
  • the content of the photopolymerization initiator in the curable resin composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the oligomer (A), the monomer (B) and the monomer (C). More preferably, it is 1 to 2.5 parts by mass.
  • a curing agent that generates radicals by heat may be blended in place of the photopolymerization initiator or in combination with the photopolymerization initiator.
  • the curable resin composition of this invention may contain the other curable monomer which does not correspond to any of a monomer (B) and a monomer (C) as needed. Moreover, you may contain the other curable oligomer which does not correspond to an oligomer (A) as needed. However, from the viewpoint of keeping the dielectric constant of the resulting cured product low, the other curable monomer is preferably a monomer having no hydroxyl group.
  • the curable resin composition of the present invention includes an oligomer (A), a monomer (B), a monomer (C), a non-curable polymer component containing a rosin ester (D), and the above-described components included as necessary.
  • the aspect which consists of a photoinitiator and the following additive is preferable.
  • the curable monomer that can be used as necessary is preferably a (meth) acrylate having one or more (meth) acryloyl groups, such as cyclohexyl (meth) acrylate, norbornene (meth) acrylate, and dicyclopentenyl (meth) acrylate.
  • a (meth) acrylate having one or more (meth) acryloyl groups such as cyclohexyl (meth) acrylate, norbornene (meth) acrylate, and dicyclopentenyl (meth) acrylate.
  • Cycloaliphatic (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate; 1,4-butanediol di (meth) acrylate and 1,6-hexanediol (meth)
  • polyfunctional acrylates such as 1,9-nonanediol di (meth) acrylate, trimethylolpropane (meth) acrylate, and pentaerythritol (meth) acrylate.
  • One or more curable monomers that can be used as needed can be used.
  • the curable oligomer that can be used as required is preferably an oligomer having at least one (meth) acryloyl group, such as di (meth) acrylate of polybutadiene diol, di (meth) acrylate of hydrogenated polybutadiene diol, polyisoprene. Examples thereof include polyfunctional (meth) acrylate oligomers having no urethane group such as di (meth) acrylate of diol.
  • One or more curable oligomers that can be used as needed can be used.
  • the curable resin composition of the present invention may contain various additives depending on applications.
  • Additives include UV absorbers (benzotriazoles, hydroxyphenyltriazines, etc.), light stabilizers (hindered amines, etc.), polymerization inhibitors (hydroquinones (2,5-di-tert-butylhydroquinone (hereinafter referred to as “hindered amines”)) ), Etc.), catechol (p-tert-butylcatechol, etc.), anthraquinone, phenothiazine, hydroxytoluene, etc.), antioxidant, tackifier (terpene tackifier) Agents, styrenic tackifiers, etc.), pigments, dyes, metal oxide fine particles, fillers and the like.
  • the ultraviolet absorber is used for preventing the photo-degradation of the curable resin composition and improving the weather resistance, for example, ultraviolet rays such as benzotriazole, triazine, benzophenone and benzoate. An absorbent etc. are mentioned.
  • benzotriazole ultraviolet absorber examples include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2,4-bis (1-methyl-1-phenylethyl) -6- (2H-benzotriazole- 2-yl) phenol, 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, (2 , 2-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3, -tetramethylbutyl) phenol], 2- (2H-benzotriazol-2-yl)- 4,6-bis (1,1-dimethyl-propyl) -phenol and the like.
  • Examples of the triazine ultraviolet absorber include 2- [4,6-diphenyl-1,3,5-triazin-2-yl] -5- (hexyloxy) phenol, 2- [4,6-bis (2 , 4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (isooctyloxy) -phenol.
  • Examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-n-octyloxybenzophenone, (2,4-dihydroxyphenyl) phenyl-methanone, and the like.
  • Examples of the benzoate ultraviolet classifier include 2- [4,6-diphenyl-1,3,5-triazin-2-yl] -5- (hexyloxy) phenol.
  • the said light stabilizer is used in order to prevent the photodegradation of a curable resin composition and to improve a weather resistance, for example, a hindered amine type light stabilizer is mentioned.
  • a hindered amine type light stabilizer examples include N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) -N ′-[4- [butyl (2,2,6,6).
  • the antioxidant is used to prevent oxidation of the curable resin composition and improve weather resistance and heat resistance, and examples thereof include phenol-based and phosphorus-based antioxidants.
  • phenolic antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2′-thiodiethylbis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N ′-(1,6-hexanediyl) Bis [3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanamide], octyl-3,5-di-tert-butyl-4-hydroxy-hydrocarbinic acid, 2,4,6- Tris (3 ′, 5′-di-tert
  • phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite , Cyclic neopentanetetrayl bis (nonylphenyl) phosphite, cyclic neopentanetetrayl bis (dinonylphenyl) phosphite, cyclic neopentanetetrayl tris (nonylphenyl) phosphite, cyclic neopentanetetrayl Tris (dinonylphenyl) phosphite, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, di
  • the curable resin composition of the present invention preferably contains no solvent.
  • volatile components such as a solvent.
  • the curable resin composition of the present invention is applied to a substrate or the like to form a coating film of the curable resin composition, the coating property is insufficient due to the high viscosity of the curable resin composition. It may be.
  • a coating property can be improved by adding a solvent to the curable resin composition of the present invention. In this case, the solvent is volatilized and removed from the curable resin composition before the curable resin composition is cured.
  • the temporary use of such a solvent does not mean that the solvent is a component of the curable resin composition of the present invention.
  • the solvent may be accompanied by the curable oligomer (A) and mixed in a small amount in the curable resin composition.
  • a small amount of low boiling point compounds may be mixed with the components of the curable resin composition. In such a case, it is preferable to remove the low boiling point solvent or the like before curing the curable resin composition, if necessary. Note that a very small amount of solvent or the like may remain in the curable resin composition as long as the curing of the curable resin composition is not adversely affected.
  • the content of other components in 100% by mass of the curable resin composition is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less.
  • the curable resin composition When using a curable resin composition of the present invention to produce a laminate by a production method using a reduced pressure lamination method described later, the area exposed to a reduced pressure atmosphere in the curable resin composition is relatively large. It is preferable that the curable resin composition does not contain a low boiling point compound. Thereby, it is suppressed that the low boiling-point compound in curable resin composition volatilizes, and a composition changes a lot. Moreover, it becomes easy to maintain a desired reduced pressure atmosphere.
  • the curable resin composition preferably does not contain a component (such as a monomer) having a boiling point of 150 ° C. or less under an atmospheric pressure atmosphere. More preferably, the lower boiling point does not contain a component having a temperature of 200 ° C. or lower.
  • the viscosity V 40 at 40 ° C. of the curable resin composition of the present invention is preferably 50 Pa ⁇ s or less, and more preferably 5 Pa ⁇ s or less. If the viscosity V 40 is more than the upper limit, sufficient fluidity can not be obtained, it bubbles hardly occurs in the curable resin composition.
  • the viscosity V 25 at 25 ° C. of the curable resin composition of the present invention is preferably 0.05 Pa ⁇ s or more, and more preferably 0.20 Pa ⁇ s or more.
  • the viscosity V 25 is preferably 4.5 Pa ⁇ s or less.
  • the viscosity V 25 is equal to or higher than the lower limit value, it is not necessary to use a large amount of low molecular weight monomer or the like in order to lower the viscosity, and thus the physical properties of the cured product are hardly lowered. If the viscosity V 25 is more than the upper limit, excellent coating properties.
  • the viscosity is a value measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85U).
  • the curable resin composition of the present invention described above contains a curable oligomer (A), a curable monomer (B), and a rosin ester (D) at specific ratios, and further includes a curable monomer ( C) may be contained in a specific ratio. Therefore, it is possible to form a cured product having a low dielectric constant and excellent moisture and heat resistance.
  • the curable resin composition of the present invention can be used for applications such as an adhesive and a coating agent in addition to the use of forming a cured resin layer in a laminate described later and the use of forming a cured resin layer in an image display device.
  • the curable resin composition of the present invention can be formed into a cured product by, for example, irradiating a curable resin composition containing the above-described amount of the above-described photopolymerization initiator with 500 mJ or more of visible light or ultraviolet rays. it can.
  • a cured product can be obtained by heating at a temperature corresponding to the half-life of the curing agent.
  • the storage elastic modulus of the cured product is preferably 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa.
  • the relative dielectric constant of the cured product at 10 kHz is preferably 3.5 or less.
  • An adhesive film can be obtained by sandwiching both sides of the cured product with a first protective film and a second protective film.
  • the first protective film and the second protective film preferably have different adhesion to the cured product.
  • the protective film include a PET (Polyethylene Terephthalate) film in which a release agent such as a silicone resin is applied to the surface in contact with the cured product, and a resin material having relatively low adhesion such as polyethylene, polypropylene, and a fluorine resin.
  • a film is preferred.
  • cured material is good also as a transparent surface material with hardened
  • the transparent surface material with a cured product preferably has a protective film on a surface different from the transparent surface material of the cured product.
  • the transparent substrate with an adhesive layer is, for example, a protective plate with an adhesive layer that is bonded to a display panel of a display device.
  • the transparent substrate include a glass plate, a chemically strengthened glass plate, a transparent resin plate (polycarbonate plate), and the like.
  • the substrate may be a multilayer structure or a single layer structure.
  • the thickness of the protective plate is 0.5 mm to 25 mm in the case of a glass plate from the viewpoint of mechanical strength and transparency.
  • the glass thickness is preferably 0.3 mm to 1.5 mm in terms of strength.
  • a transparent resin plate is used as the protective plate, it is preferably 2 mm to 10 mm.
  • the curable resin composition of the present invention can be suitably used for forming a cured resin layer in a laminate having a pair of substrates and a cured resin layer sandwiched between the pair of substrates.
  • a laminate in which a display device and a transparent substrate opposed to the viewing surface side of the display device are regarded as a pair of substrates, and the pair of substrates are both transparent substrates.
  • a certain transparent laminated body etc. are mentioned.
  • substrate which comprises a laminated body both a transparent substrate and an opaque board
  • substrate can be used as a board
  • substrate can be used as a board
  • substrate can be used as a board
  • the substrate may be a multilayer structure or a single layer structure.
  • the curable resin composition of the present invention is an image display device in which a transparent substrate such as a touch panel or a protective plate is laminated on a display device such as a liquid crystal display device via a cured resin layer. It can be used suitably for formation.
  • Examples of the display device include a liquid crystal display device, an organic EL display device, a plasma display device, and an electronic ink display device. These display devices are usually multilayer structures and are opaque as a whole. Therefore, a stacked body in which a display device and a transparent substrate opposed to the viewing surface side of the display device are regarded as a pair of substrates is an opaque stacked body.
  • the display device is usually a multilayer structure, and the display layer (liquid crystal layer, organic EL layer, etc.) and the layer closer to the non-viewing surface than the display layer are opaque, but more visible than the display layer.
  • the surface side layer is usually transparent.
  • the surface layer on the viewing surface side of the display device (for example, the outermost layer such as a layer made of a polarizing plate or a layer made of an optical film such as a retardation plate in a liquid crystal display device) is protected transparently through a cured resin layer.
  • the surface layer on the viewing surface side of the display device is regarded as one substrate and the protective plate is regarded as the other substrate, the surface layer / cured resin layer / protective plate
  • the resulting laminate can be considered a transparent laminate.
  • a cured resin layer can be formed by irradiating the curable resin composition sandwiched between the substrates through the transparent substrate.
  • the cured resin layer can be formed by heating and curing the curable resin composition.
  • the image display device of the present invention is an image display device having one or more cured resin layers obtained by curing the curable resin composition of the present invention.
  • the cured resin layer acts as an adhesive layer such as between the display device and the touch panel and an adhesive layer such as between the touch panel and a transparent substrate such as a protective plate.
  • the cured resin layer obtained by curing the curable resin composition of the present invention can be provided between any plate-like or film-like members constituting the image display device. it can.
  • the curable resin composition of the present invention has an appropriate viscosity and excellent applicability, and the formed cured resin layer has an appropriate elastic modulus and adhesiveness that can adhere an object well, heat resistance, Appearance (transparency), moisture and heat resistance. Therefore, it is suitable for forming a cured resin layer in a laminate or an image display device in which a display device and a transparent substrate opposed to the viewing surface of the display device are regarded as a pair of substrates.
  • the cured resin layer is used as the curable resin composition of the present invention. Since the cured product has a low dielectric constant, malfunction of the touch panel due to electromagnetic waves generated from the liquid crystal display device can be prevented. Therefore, in the image display device having such a configuration, the effect obtained by using the curable resin composition of the present invention is great.
  • the cured resin layer is a layer made of a cured product of the curable resin composition of the present invention.
  • the thickness of the cured resin layer is preferably 0.01 to 0.5 mm, more preferably 0.05 to 0.3 mm. If the thickness of a cured resin layer is more than a lower limit, the mechanical strength of a laminated body will become favorable. If the thickness of a cured resin layer is below an upper limit, a laminated body will become lightweight.
  • the cured resin layer sandwiched between a pair of substrates is made of a cured product of the curable resin composition of the present invention, the dielectric constant is low, the moisture and heat resistance is excellent, A cured resin layer having elasticity and flexibility is provided.
  • the above laminate is preferably produced by a production method using a reduced pressure lamination method.
  • the reduced pressure lamination method is disclosed in International Publication No. 2008/081838 and International Publication No. 2009/016943.
  • the laminate of the present invention that is, the laminate in which the display device and the transparent substrate opposed to the viewing surface side of the display device are regarded as a pair of substrates, for example, includes the following first step and second step. It can manufacture by the method which has these processes.
  • First step In a reduced pressure atmosphere, the curable resin composition of the present invention is sandwiched between a pair of substrates, and the periphery of the curable resin composition between the pair of substrates is sealed with a sealing material. To form a hermetically sealed laminated precursor.
  • 2nd process The said curable resin composition of the said lamination
  • (First step) It is not necessary to perform all the operations in the first step under a reduced-pressure atmosphere as long as the curable resin composition is sealed in a reduced-pressure atmosphere to be a laminated precursor.
  • a sealing material is provided on the entire periphery of one substrate and the other substrate is stacked after the curable resin composition is supplied to the inside of the sealing material on the substrate, the other substrate is stacked.
  • the previous work may be performed under an atmospheric pressure atmosphere.
  • the sealing material include a double-sided adhesive tape and the curable resin composition of the present invention.
  • the pressure atmosphere in the first step is preferably a pressure atmosphere of 1 kPa or less, and more preferably a pressure atmosphere of 100 Pa or less. Moreover, since the low boiling point compound in the curable resin composition may volatilize if the pressure in the reduced pressure atmosphere is too low, the reduced pressure atmosphere is preferably a pressure atmosphere of 1 Pa or more, and more preferably a pressure atmosphere of 10 Pa or more. .
  • the adhesion strength between the pair of substrates and the sealing material is within a range in which gas does not enter from the interface between the substrate and the sealing material when the lamination precursor is placed in an atmosphere having a pressure higher than the reduced-pressure atmosphere in the second step.
  • the adhesion strength between the substrate and the sealing material can be increased by using a pressure sensitive adhesive.
  • substrate and a sealing material can be raised by interposing a curable adhesive in the interface of a board
  • the adhesion strength between the substrate and the sealing material can also be increased by forming the sealing material with a curable resin and curing the sealing material itself after forming the laminated precursor.
  • the curable resin composition in the lamination precursor is cured in an atmosphere at a pressure higher than the reduced pressure atmosphere in the first step.
  • the curable resin composition is thermosetting, it is cured by heating, and when the curable resin composition is photocurable, it is cured by light irradiation.
  • Photocuring can be performed by irradiating light through a transparent substrate from a light source such as an ultraviolet lamp.
  • the cured resin layer is formed by curing the curable resin composition, and a laminate is obtained.
  • a photopolymerization initiator is blended in the curable resin composition and the curable resin composition is cured by light irradiation in the second step.
  • the production method even if bubbles remain in the curable resin composition in the first step, the bubbles are likely to disappear before the curable resin composition is cured in the second step. No cured resin layer is easily formed. This is due to the following factors.
  • the laminated precursor formed in the first step is placed in a pressure atmosphere higher than the reduced pressure atmosphere of the first step in the second step, the pressure outside the transparent substrate becomes larger than the pressure inside, Pressure is applied to the curable resin composition from the substrate.
  • the inside of the bubbles in the curable resin composition is at the pressure of the reduced pressure atmosphere in the first step, the volume of the bubbles is reduced by the pressure applied to the curable resin composition in the second step, or When the gas in the bubbles dissolves in the curable resin composition, the bubbles disappear.
  • the laminated precursor in the second step, before curing the curable resin composition, is held for a while under a pressure atmosphere higher than the reduced-pressure atmosphere. It is preferable to do.
  • the holding time is preferably 5 minutes or more. Note that the holding time may be less than 5 minutes when there are no bubbles or when the bubbles are minute and disappear quickly.
  • the atmosphere having a higher pressure than the reduced-pressure atmosphere in the second step is preferably a pressure atmosphere of 50 kPa or more, more preferably a pressure atmosphere of 100 kPa or more, and an atmospheric pressure atmosphere is particularly preferable from the viewpoint of easy control of the pressure atmosphere.
  • the pressure atmosphere in the first step and the second step is particularly preferably a pressure atmosphere of 100 Pa or less in the first step and an atmospheric pressure atmosphere in the second step.
  • a sealing material 12 is provided over the entire periphery of one substrate 10 (hereinafter simply referred to as “substrate 10”), and a sealing UV curable resin 36 is applied on the sealing material 12.
  • the curable resin composition 14 is supplied to the surface of the substrate 10 surrounded by the sealing material 12.
  • the layer of the curable resin composition 14 is placed horizontally in the decompression chamber 26 with the layer facing up.
  • the other substrate 16 (hereinafter simply referred to as “substrate 16”) is held by the suction pad 32 on the upper surface plate 30 that can be moved up and down by the cylinder 34 in the decompression chamber 26, and in parallel above the substrate 10.
  • the decompression chamber 26 is closed, and the vacuum pump 28 is operated to evacuate, so that the inside of the decompression chamber 26 has a predetermined decompressed atmosphere. Thereafter, the cylinder 34 is operated to lower the substrate 16, the layer of the curable resin composition 14 is sandwiched between the substrate 10 and the substrate 16, and the curable resin composition 14 is sealed by the substrate 10, the substrate 16, and the sealing material 12. A laminated precursor is formed.
  • the reduced pressure chamber 26 is returned to the atmospheric pressure atmosphere, the laminated precursor is taken out from the reduced pressure chamber 26, and the curable resin composition of the laminated precursor is heated or irradiated with light in the atmospheric pressure atmosphere. It hardens
  • symbol 21 is a cured resin layer
  • symbol 31 is a weir-like part which consists of a sealing material and the hardened
  • a laminated body can be manufactured with high productivity.
  • DBTDL dibutyltin dilaurate
  • HOA 2-hydroxyethyl acrylate
  • the molar ratio (equivalent ratio) of the isocyanate group of the prepolymer (P-1) to the hydroxyl group of the curable monomer (a3) was 1: 1.02.
  • the number average molecular weight of the obtained oligomer (A1-1) was 21,180, and the average number of curable groups (acryloyl groups) per molecule was 1.9.
  • this average number was calculated
  • prepolymer (P-2) an isocyanate group-terminated prepolymer (prepolymer (P-2)).
  • the index of polyisocyanate (a2) relative to polydiene polyol (a1) was 150.
  • the isocyanate group content of the prepolymer (P-2) was 1.518% by mass.
  • the molar ratio of the isocyanate group of the prepolymer (P-3) to the hydroxyl group of (HEA + 1-octanol) was 1: 1.02.
  • the number average molecular weight of the obtained oligomer (A1-3) was 22,590, and the average number of curable groups (acryloyl groups) per molecule was 1.7.
  • prepolymer (P-4) an isocyanate group-terminated prepolymer (prepolymer (P-4)).
  • index of polyisocyanate (a2) relative to polydiene polyol (a1) was 116.
  • the isocyanate group content of the prepolymer (P-4) was 0.7077% by mass.
  • prepolymer (P-4) isocyanate group amount: 0.0240 mol
  • 0.00929 g of DBTDL, 0.046 g of DtBHQ, and 2.20 g of HEA as a curable monomer (a3) hydroxyl group amount: 0.0189 mol
  • 0.7322 g of 1-octanol hydroxyl content: 0.0056 mol
  • the molar ratio of the isocyanate group of the prepolymer (P-4) to the hydroxyl group of (HEA + 1-octanol) was 1: 1.02.
  • the number average molecular weight of the obtained oligomer (A1-4) was 15,470, and the average number of curable groups (acryloyl groups) per molecule was 1.6.
  • n 1 isocyanate group content n 1 (mass%) is measured.
  • the n 1 remains when all of the isocyanate groups have reacted.
  • the reaction was terminated, and a prepolymer was obtained.
  • the IPDI index for polypropylene glycol was 122.
  • the isocyanate group content of the prepolymer (P-5) was 0.244% by mass.
  • prepolymer (P-6) a hydroxyl group-terminated urethane prepolymer (prepolymer (P-6)).
  • index of polyisocyanate (a2) relative to polydiene polyol (a1) was 58.
  • the isocyanate group content of the prepolymer (P-6) was 0.00% by mass.
  • Examples 1 to 18 and Comparative Examples 1 to 10 The oligomers obtained in each of the production examples and other components were mixed at the compounding ratios shown in Tables 1 to 5, and curable resin compositions (J-1 to 18 (Examples), H-1 to 10) were mixed. (Comparative example) was prepared. Each curable resin composition obtained and its cured product were evaluated by the following methods. The relative dielectric constant was measured only for the examples shown in Table 6. The evaluation results are shown in Tables 1 to 5 and Table 6.
  • ACMO 4-acryloylmorpholine
  • M-600A 2-hydroxy-3-phenoxypropyl acrylate
  • 4-HBA 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., product name: 4-HBA).
  • HEA 2-hydroxyethyl acrylate (reagent manufactured by Wako Pure Chemical Industries, Ltd.).
  • IBXA Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., product name: IBXA).
  • LA Lauryl acrylate (manufactured by Osaka Organic Chemical Industry, product name: LA).
  • KE-311 Rosin ester (manufactured by Arakawa Chemical Co., Ltd., product name: KE-311, color number: Hazen 40, acid value: 7.0 mgKOH / g, softening point: 99 ° C.)
  • PE-590 Hydrogenated rosin ester (manufactured by Arakawa Chemical Co., Ltd., product name: Pine Crystal PE-590.
  • RIC156 Polybutadiene (manufactured by CRAY VALLEY, product name: Ricon156, 1,4 bond amount: 35%, number average molecular weight: 1,400).
  • R-15HT Polybutadiene polyol (manufactured by Idemitsu Kosan Co., Ltd., product name: Poly bd R-15HT, 1,4 bond amount: 80%, number average molecular weight: 1,200).
  • PB polybutadiene (manufactured by Aldrich, 1,4 bond amount: 99%, number average molecular weight: 1,800).
  • HV-15 Polybutene (manufactured by JX Nippon Mining & Energy, product name: Nippon Polybutene HV-15, number average molecular weight 630).
  • LV-100 Polybutene (manufactured by JX Nippon Mining & Energy, product name: Nisshi Polybutene LV-100, number average molecular weight: 500).
  • PML 5005 polyoxypropylene glycol (manufactured by Asahi Glass Co., Ltd., product name: PREMINOL 5005).
  • BAC-45 polybutadiene-terminated diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., product name: BAC-45).
  • Irg819 Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, product name: Irgacure-819).
  • Irg184 Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, product name: Irgacure-184).
  • IrgTPO 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, product name: Irgacure-TPO).
  • DtBHQ 2,5-di-tert-butylhydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • PUR68 Stabilizer mixture (manufactured by BASF, product name: IRGACURE PUR68).
  • Irg1520 4,6-bis (octylthiomethyl) -o-cresol (manufactured by BASF, product name: Irganox-1520L).
  • the viscosity is preferably 4,500 mPa ⁇ s or less for practical use.
  • the curable resin composition obtained in each example was applied to a thickness of 0.4 mm, and ultraviolet light (light source: manufactured by Ushio Inc., mercury xenon lamp, illuminance: 100 mW / cm 2) under nitrogen flow. , Integrated light amount: 6,000 mJ / cm 2 ) was irradiated and cured to obtain a cured product.
  • the specific gravity of the curable resin composition before curing (specific gravity before curing) and the specific gravity of the cured product after curing (cured product specific gravity), an electronic balance with a specific gravity measurement kit (manufactured by Sartorius, product name) : CPA224S), and the curing shrinkage (unit:%) was calculated from the following formula based on the specific gravity difference before and after curing.
  • Curing shrinkage (%) (cured product specific gravity ⁇ specific gravity before curing) / specific gravity before curing ⁇ 100
  • the curing shrinkage rate (%) is preferably 2.0% or less for practical use.
  • the position of the spindle was automatically adjusted so that no stress was generated in the normal direction of the spindle when the curable resin composition was cured.
  • the irradiation intensity was measured on a stage on which the curable resin composition was installed using an illuminance meter (Ushio Electric Co., Ltd., UV intensity meter Unimeter UIT-101).
  • the curable resin composition obtained in each example was applied to a thickness of 0.4 mm, and ultraviolet light (light source: manufactured by Ushio Inc., mercury xenon lamp, illuminance: 100 mW / cm 2) under nitrogen flow. , Accumulated light amount: 3,000 mJ / cm 2 ) and cured.
  • the cured sample was cut into a circle having a diameter of 38 mm, and then the relative dielectric constant of 10 kHz was measured using a 6440B LCR meter manufactured by Weinker.
  • the curable resin composition obtained in each example was applied on a 2 mm thick soda lime glass so as to have a thickness of 0.1 mm, and a 2 mm thick soda lime glass was further laminated thereon to obtain a laminated sample.
  • the laminated sample was irradiated with ultraviolet rays (light source: metal halide lamp manufactured by ORC, illuminance: 100 mW / cm 2 , integrated light amount: 3000 mJ / cm 2 ).
  • the laminated sample after irradiation with ultraviolet rays was left under conditions of a temperature of 65 ° C.
  • ⁇ (good) The haze of the laminated sample is 0.5% or less.
  • X (defect) The haze of the laminated sample exceeds 0.5%. The haze value was measured after leaving the laminated sample at room temperature for 2 hours using a Nippon Denshoku Co., Ltd./color turbidity simultaneous measuring device COH400.
  • a laminated sample was prepared and irradiated with ultraviolet rays in the same manner as in the evaluation of the heat and humidity resistance.
  • the laminated sample after irradiation with ultraviolet rays was allowed to stand at a temperature of 80 ° C., and after 500 hours, the heat resistance was evaluated according to the following criteria. “ ⁇ (good)”: peeled off from the laminated sample, no generation of bubbles, and YI of 2.0 or less “X (defect)”: any of occurrence of peeling, generation of bubbles, and YI exceeding 2.0 in the laminated sample is recognized.
  • the YI value was measured using a color turbidity simultaneous measuring device COH400 manufactured by Nippon Denshoku Co., Ltd., and after leaving the laminated sample at room temperature for 2 hours.
  • the curable resin composition of each example had a viscosity in an appropriate range and the appearance was transparent. Further, the cured product had a low relative dielectric constant and excellent heat and humidity resistance. Furthermore, the cured product had an elastic modulus in an appropriate range, a small shrinkage in curing, and excellent adhesion and heat resistance.
  • the curable resin composition of the present invention can form a cured product having a low dielectric constant and excellent moisture and heat resistance. Therefore, the curable resin composition of the present invention is suitable for forming a cured resin layer provided between a pair of substrates. Moreover, the curable resin composition of this invention can be used also for uses, such as an adhesive agent and a coating agent.
  • the curable resin composition of the present invention is a transparent substrate such as a touch panel and a protective plate between the display device and the touch panel in an image display device in which a touch panel and a protective plate are laminated on a display device such as a liquid crystal display device. It is also suitably used for forming a curable resin layer provided as an adhesive layer between the two. It should be noted that the entire content of the specification, claims, abstract, and drawings of Japanese Patent Application No. 2014-9655 filed on January 22, 2014 is cited here as the disclosure of the specification of the present invention. Incorporated.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)
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Abstract

　La présente invention concerne une composition de résine durcissable selon laquelle un matériau durci ayant une faible permittivité et une excellente résistance à la chaleur humide peut être formé, ainsi qu'un corps stratifié et un dispositif d'affichage d'images qui utilisent la composition de résine durcissable. L'invention concerne une composition de résine durcissable contenant, selon un rapport spécifique, un oligomère durcissable (A) possédant une chaîne polybutadiène et/ou une chaîne polyisoprène, un monomère durcissable (B) qui est composé amine tertiaire possédant un groupe (méth)acryloyl, une colophane estérifiée (D), et , facultativement, un monomère durcissable (C) qui est un (méth)acrylate d'akyle dans lequel la partie formant groupe alkyle possède un nombre de carbones allant de 8 à 22.
PCT/JP2015/051413 2014-01-22 2015-01-20 Composition de résine durcissable et corps stratifié et dispositif d'affichage d'images utilisant la composition de résine durcissable WO2015111584A1 (fr)

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JP2015214594A (ja) * 2014-05-07 2015-12-03 昭和電工株式会社 重合性組成物、重合物、光学用粘着シート、画像表示装置およびその製造方法
WO2016080084A1 (fr) * 2014-11-20 2016-05-26 協立化学産業株式会社 Composition de résine photodurcissable
JP2017043642A (ja) * 2015-08-24 2017-03-02 アイカ工業株式会社 ガスケット用光硬化樹脂組成物
WO2017038845A1 (fr) * 2015-09-01 2017-03-09 デクセリアルズ株式会社 Composition de résine photodurcissable et procédé de fabrication de dispositif d'affichage d'image
JP2017048358A (ja) * 2015-09-01 2017-03-09 デクセリアルズ株式会社 光硬化性樹脂組成物、及び画像表示装置の製造方法
WO2017073584A1 (fr) * 2015-10-27 2017-05-04 日本化薬株式会社 Composition de résine durcissable par les ultraviolets pour écrans tactiles, produit durci l'utilisant et écran tactile
JP2017102386A (ja) * 2015-12-04 2017-06-08 株式会社ジャパンディスプレイ 表示装置
JP2019182929A (ja) * 2018-04-03 2019-10-24 王子ホールディングス株式会社 粘着剤組成物、粘着シート及び積層体

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WO2013088889A1 (fr) * 2011-12-13 2013-06-20 昭和電工株式会社 Procédé de production de feuille adhésive transparente double face, et feuille adhésive transparente double face
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JP2015214594A (ja) * 2014-05-07 2015-12-03 昭和電工株式会社 重合性組成物、重合物、光学用粘着シート、画像表示装置およびその製造方法
WO2016080084A1 (fr) * 2014-11-20 2016-05-26 協立化学産業株式会社 Composition de résine photodurcissable
JP2016098304A (ja) * 2014-11-20 2016-05-30 協立化学産業株式会社 光硬化性樹脂組成物
JP2017043642A (ja) * 2015-08-24 2017-03-02 アイカ工業株式会社 ガスケット用光硬化樹脂組成物
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WO2017038845A1 (fr) * 2015-09-01 2017-03-09 デクセリアルズ株式会社 Composition de résine photodurcissable et procédé de fabrication de dispositif d'affichage d'image
KR102031528B1 (ko) 2015-09-01 2019-10-14 데쿠세리아루즈 가부시키가이샤 광 경화성 수지 조성물, 및 화상 표시 장치의 제조 방법
WO2017073584A1 (fr) * 2015-10-27 2017-05-04 日本化薬株式会社 Composition de résine durcissable par les ultraviolets pour écrans tactiles, produit durci l'utilisant et écran tactile
JPWO2017073584A1 (ja) * 2015-10-27 2018-08-09 日本化薬株式会社 タッチパネル用紫外線硬化型樹脂組成物、それを用いた硬化物及びタッチパネル
JP2017102386A (ja) * 2015-12-04 2017-06-08 株式会社ジャパンディスプレイ 表示装置
JP2019182929A (ja) * 2018-04-03 2019-10-24 王子ホールディングス株式会社 粘着剤組成物、粘着シート及び積層体
JP7059762B2 (ja) 2018-04-03 2022-04-26 王子ホールディングス株式会社 粘着剤組成物、粘着シート及び積層体

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