WO2015181984A1 - Composition de résine photodurcissable - Google Patents

Composition de résine photodurcissable Download PDF

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Publication number
WO2015181984A1
WO2015181984A1 PCT/JP2014/064534 JP2014064534W WO2015181984A1 WO 2015181984 A1 WO2015181984 A1 WO 2015181984A1 JP 2014064534 W JP2014064534 W JP 2014064534W WO 2015181984 A1 WO2015181984 A1 WO 2015181984A1
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WO
WIPO (PCT)
Prior art keywords
component
meth
resin composition
acrylate
photocurable resin
Prior art date
Application number
PCT/JP2014/064534
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English (en)
Japanese (ja)
Inventor
慶次 後藤
健司 深尾
貴子 星野
公彦 依田
Original Assignee
電気化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to CN201480079438.1A priority Critical patent/CN106414525B/zh
Priority to JP2016523085A priority patent/JPWO2015181984A1/ja
Priority to PCT/JP2014/064534 priority patent/WO2015181984A1/fr
Priority to KR1020167033667A priority patent/KR102206665B1/ko
Publication of WO2015181984A1 publication Critical patent/WO2015181984A1/fr

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Classifications

    • 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
    • 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
    • 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
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety

Definitions

  • the present invention relates to a photocurable resin composition.
  • a coating layer made of an inorganic material or an organic material is provided on the surfaces of glass, films and sheets used for sensor elements such as CCDs and CMOSs and display elements such as displays.
  • a coating layer or the like in which a high refractive index layer and a low refractive index layer are alternately laminated is used for the purpose of imparting functions such as antireflection and optical waveguide to the surface protective layer.
  • This high refractive index layer contains a high refractive index inorganic film formed by vapor deposition of ceramics such as titania, zirconia and alumina, and radical polymerizable monomers such as bisphenol A type epoxy (meth) acrylate and urethane (meth) acrylate.
  • a high refractive index organic film that is irradiated with an energy ray such as ultraviolet rays to form a cured film is used depending on the purpose.
  • an energy ray such as ultraviolet rays to form a cured film
  • the substrate is a film or sheet
  • problems such as insufficient adhesion, and the film is fragile and breaks when the film is bent.
  • a photo-curing type high refractive index organic film containing a radical polymerizable monomer has been widely used.
  • Patent Documents 1 to 3 An adhesive composition and a photo-curable resin composition using the above are known (Patent Documents 1 to 3).
  • Patent Document 4 discloses an active energy ray-curable composition using urethane (meth) acrylate having a diphenylsulfone structure.
  • Patent Documents 5 to 9 have a description that monofunctional (meth) acrylate can be used for the purpose of dilution or the like.
  • sulfur-containing (meth) acrylates urethane (meth) acrylates having a diphenylsulfone structure, and 4,4′-dimercaptodiphenyl sulfide dimethacrylate, which are the main components described in Patent Documents 1 to 4, are bisphenol A type Although it has a higher refractive index than compounds having an aromatic ring such as epoxy (meth) acrylate, these compounds generally absorb light with a wavelength of 450 nm or less, so they are colored yellow and transparency tends to decrease. There was a problem that it was difficult to adhere to the film.
  • Example of patent document 5 uses the dimethacrylate and / or bisphenol F ethylene oxide modified acrylate which have ethylene glycol chain as components other than the (meth) acrylate which has a fluorene skeleton, adhesiveness, light resistance There was a problem of low nature.
  • Example of patent document 6 uses the monofunctional (meth) acrylate compound which has two aromatic rings as components other than the (meth) acrylate which has a fluorene skeleton, although a high refractive index is obtained. There are problems such as low adhesion, transparency and light resistance.
  • alkali-soluble resins and silica fine particles which are (meth) acrylate copolymers having a carboxyl group and an ethylenically unsaturated group in the molecule, as components other than (meth) acrylate having a fluorene skeleton are used. Since it was used, there was a problem that the refractive index was lowered.
  • Example of patent document 9 uses the polyfunctional curable monomer which has a 3 or more (meth) acryloyl group in a molecule
  • numerator as components other than (meth) acrylate which has a fluorene skeleton
  • adhesiveness There was a problem that adhesiveness was low.
  • Patent Documents 5 to 9 do not describe the composition ratio of monofunctional (meth) acrylate.
  • the present invention has been made in view of such circumstances.
  • the present invention uses a specific amount of monofunctional (meth) acrylate.
  • the present invention provides a photocurable resin composition having a high refractive index and high transparency and a short fixing time.
  • a fluorene compound represented by the following general formula (1) (In the general formula (1), R 1 , R 2 , R 3 , and R 4 each represent a hydrogen atom or a methyl group, and a and b each represent an integer of 1 to 4. Note that each substituent is a benzene ring.
  • the content of the component (A) is 10 to 70 parts by mass
  • the content of the component (B) is 5 to 65 parts by mass.
  • a content ratio of the component (C) is 5 to 65 parts by mass.
  • the glass transition temperature of a homopolymer is 40 degreeC or more and 180 degrees C or less.
  • a silane coupling agent as a component (E).
  • the component (E) is preferably a silane coupling agent having one or more functional groups selected from a phenyl group or a (meth) acryloyl group.
  • the liquid refractive index at a temperature of 25 ° C. and a wavelength of 589 nm is preferably 1.50 or more, and the cured product refractive index is preferably 1.53 or more. It is preferable that it is a coating material which consists of a ⁇ 6> photocurable resin composition. It is preferable that it is a base material which has a ⁇ 7> coating material.
  • a substrate having a film is preferred. It is preferable that it is an element which has a ⁇ 10> base material. It is preferable that it is an adhesive agent which consists of a ⁇ 11> photocurable resin composition.
  • a bonded body bonded with an adhesive is preferable.
  • An optical component having a joined body is preferable.
  • the inventors of the present application conducted research and development on a photocurable resin composition using the fluorene-based compound represented by the general formula (1).
  • a photocurable resin composition of the above fluorene compound was created.
  • the effects described above are obtained by mixing a monofunctional (meth) acrylate having an alicyclic hydrocarbon group and a monofunctional (meth) acrylate having one aromatic ring in a specific content ratio.
  • the present invention was completed by clarifying that a photo-curable resin composition exhibiting the above can be obtained.
  • the present invention has the effects of having a high refractive index and high transparency and a short fixing time.
  • the covering material is to impart surface protection, designability, or functionality such as antireflection or optical waveguide on a substrate such as a glass substrate, a plastic film, or a plastic sheet. It means a material coated for the purpose.
  • the adhesive means an adhesive for bonding components to each other, particularly an adhesive suitably used for bonding optical components.
  • the total of the components (A) to (C) is preferably 70 parts by mass or more, and 90 parts by mass or more in 100 parts by mass of the photocurable resin composition. More preferably, it is 93 parts by mass or more, still more preferably 95 parts by mass or more.
  • the total of the components (A) to (C) is, for example, 60, 65, 70, 75, 80, 85, 88 in 100 parts by mass of the photocurable resin composition. , 90, 92, 93, 95, 96, 97, 98, 99, or 100 parts by mass, or any of these two values.
  • the resin composition of this embodiment has a fluorene compound represented by the following general formula (1) as the component (A).
  • R 1 , R 2 , R 3 , and R 4 each represent a hydrogen atom or a methyl group, and a and b each represent an integer of 1 to 4. Note that each substituent is a benzene ring. It may be bonded to any substitutable carbon atom.
  • fluorene compounds include 9,9-bis [(meth) acryloyloxyphenyl] fluorenes such as 9,9-bis [4-((meth) acryloyloxy) phenyl] fluorene; 9,9-bis [4 9,9-bis [((meth) acryloyloxy such as-(2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) phenyl] fluorene C2-4 alkoxy) phenyl] fluorenes; 9,9-bis [3-methyl-4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (2 -(Meth) acryloyloxypropoxy) phenyl] fluorene, 9,9-bis [3,5-dimethyl-4- (2- (meth)
  • C refers to carbon.
  • C1-4 means having 1 to 4 carbon atoms.
  • the content of the component (A) is preferably 10 to 70 parts by mass with respect to the total amount of the resin composition (100 parts by mass in total of (A) to (C)) in terms of refractive index, transparency and adhesion. 20 to 60 parts by mass is more preferable, and 30 to 50 parts by mass is most preferable.
  • the content rate of the said (A) component may be 10, 20, 30, 40, 50, 60, or 70 mass parts, for example, and may exist in the range of those two values.
  • fluorene compound those produced by a known production method can be used. Specifically, an oxsol series manufactured by Osaka Gas Chemical Company, “NK Ester A-BPFE” manufactured by Shin-Nakamura Chemical Co., Ltd., or the like can be used.
  • the resin composition of this embodiment contains the monofunctional (meth) acrylate which has an alicyclic hydrocarbon group as (B) component.
  • Examples of the monofunctional (meth) acrylate include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, and isobornyl.
  • One or more members selected from the group consisting of acrylate, dicyclopentenyloxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate are preferred.
  • Isobornyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, dicyclopenta One or more members selected from the group consisting of nyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate are more preferable.
  • the component (B) preferably has a glass transition temperature (hereinafter referred to as Tg) of 40 ° C. or higher and 180 ° C. or lower in terms of adhesion and light resistance.
  • Tg glass transition temperature
  • Tg glass transition temperature
  • the glass transition temperature can be measured by a known method such as a differential calorimeter (hereinafter referred to as DSC) or dynamic viscoelasticity (hereinafter referred to as DMA), but measurement using DSC is preferable.
  • DSC differential calorimeter
  • DMA dynamic viscoelasticity
  • the content of the component (B) is 5 to 65 with respect to the total amount of the resin composition (total 100 parts by mass of (A) to (C)) in terms of refractive index, transparency, and adhesion to the substrate. Part by mass is preferred, 15 to 55 parts by mass is more preferred, and 25 to 45 parts by mass is most preferred.
  • the content ratio of the component (B) may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65 parts by mass, or any of them. It may be within a range of two values.
  • ⁇ (C) component monofunctional (meth) acrylate having an aromatic ring>
  • the resin composition of this embodiment contains a monofunctional (meth) acrylate having one aromatic ring for the purpose of further increasing the refractive index as the component (C).
  • Examples of the monofunctional (meth) acrylate having one aromatic ring include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, and phenoxyhexaethylene glycol.
  • benzyl (meth) acrylate and / or phenoxyethyl (meth) acrylate are preferable in view of compatibility with the component (A), refractive index, and transparency.
  • the content ratio of the component (C) is 5 to 65 masses with respect to the total amount of the resin composition (100 mass parts in total of (A) to (C)) in terms of refractive index, transparency, adhesion, and light resistance. Part is preferred, 10 to 55 parts by weight is more preferred, and 15 to 45 parts by weight is most preferred.
  • the content ratio of the component (C) may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65 parts by mass. It may be within a range of two values.
  • the resin composition of the present embodiment contains (D) a radical photopolymerization initiator.
  • the radical photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals when irradiated with energy rays.
  • photo radical polymerization initiator examples include benzyl derivatives such as benzyl, benzoin, benzoin benzoic acid, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzophenone derivatives such as benzophenone and 4-phenylbenzophenone, and 2,2-diethoxy Alkylacetophenone derivatives such as acetophenone, benzyldimethyl ketal, 1-hydroxy-cyclohexyl phenyl ketone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) ⁇ -hydroxyacetophenone derivatives such as) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc.
  • benzyl derivatives such as benzyl, benzoin, benzoin benzoic acid, benzoin
  • Acylphosphine oxide derivatives 1,2-octanedione, 1-[-4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) And oxime ester compounds such as -9H-carbazol-3-yl] -1- (O-acetyloxime).
  • at least one kind of alkyl acetophenone derivative, ⁇ -hydroxyacetophenone derivative, and acylphosphine oxide derivative is preferable from the viewpoint of excellent reactivity and transparency. These can be used alone or in combination of two or more.
  • the content ratio of the component (D) is preferably 0.1 to 10 parts by weight, and preferably 0.5 to 5 parts by weight with respect to the total amount of the resin composition (total 100 parts by weight of (A) to (C)). More preferred. If it is in the range of 0.1 to 10 parts by mass, the curability will not be deteriorated and the transparency will not be lowered.
  • the content rate of the said (D) component may be 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 mass parts, for example, It may be within the range of any two values.
  • the resin composition can further contain a silane coupling agent as the component (E) for the purpose of further improving the adhesion to the glass surface.
  • Silane coupling includes ⁇ -chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -Acryloyloxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoe
  • (meth) acryloyl 1 or more types in the group which consists of the silane coupling agent which has a (meth) acryloyl group, the silane coupling agent which has an epoxy group, and the silane coupling agent which has a phenyl group is preferable, (meth) acryloyl
  • One or more members selected from the group consisting of a silane coupling agent having a group and a silane coupling agent having a phenyl group are more preferred.
  • the silane coupling agent having a (meth) acryloyl group include ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -acryloyloxypropyltrimethoxysilane, and the like.
  • silane coupling agent having an epoxy group examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
  • silane coupling agent having a phenyl group examples include phenyltrimethoxysilane and phenyltriethoxysilane.
  • the content ratio of the component (E) is 0.1 to 10 parts by mass with respect to the total amount of the resin composition (total 100 parts by mass of (A) to (C)) in terms of refractive index, transparency and adhesion. Is preferable, and 0.5 to 5 parts by mass is more preferable.
  • the content rate of the said (E) component may be 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 mass parts, for example, It may be within the range of any two values.
  • the resin composition of the present embodiment may contain a monofunctional (meth) acrylate compound other than the above or a polyfunctional (meth) acrylate as long as the effects of the present embodiment are not impaired.
  • the method for producing the resin composition according to this embodiment is not particularly limited as long as the above materials can be sufficiently mixed.
  • the mixing method of the material is not particularly limited, and examples thereof include a stirring method using a stirring force accompanying rotation of a propeller, a method using a normal disperser such as a planetary stirrer by rotation and revolution, and the like. These mixing methods are preferable because stable mixing can be performed at low cost.
  • the resin composition can be cured by irradiation with energy rays using the following light source.
  • the light source used for curing the resin composition is not particularly limited, but is a halogen lamp, a metal halide lamp, a high-power metal halide lamp (containing indium or the like), a low-pressure mercury lamp, a high-pressure mercury lamp, or an ultra-high pressure.
  • LED light emitting diode
  • the above light sources have different emission wavelengths and energy distributions. Therefore, the light source is appropriately selected depending on the reaction wavelength of the photopolymerization initiator. Natural light (sunlight) can also be a reaction initiation light source.
  • the light source may perform direct irradiation, focused irradiation with a reflecting mirror or the like, or focused irradiation with a fiber or the like.
  • a low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like can also be used.
  • the resin composition having the above-mentioned structure is quickly cured by irradiation with energy rays, a cured product excellent in optical properties such as high transparency and high refractive index can be provided.
  • the refractive index of the resin composition is preferably a liquid refractive index at a temperature of 25 ° C. and a wavelength of 589 nm of 1.50 or more, more preferably 1.51 or more. Most preferred is .52 or more.
  • the refractive index of the resin composition is preferably a cured product refractive index at a temperature of 25 ° C. and a wavelength of 589 nm of 1.53 or more, more preferably 1.54 or more, Most preferably, it is 1.55 or more.
  • the refractive index can be measured by a known method such as an Abbe refractometer, a prism coupler, or an ellipsometer. Among these, measurement using an Abbe refractometer is preferable.
  • the resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, and has excellent adhesion to substrates such as glass, plastic film, plastic sheet, etc. can do.
  • the resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, and therefore can be used as a high refractive index layer of an antireflection film or an optical waveguide film. Therefore, the resin composition having the above configuration can provide an excellent antireflection film or optical waveguide film.
  • the antireflection film and the optical waveguide film are formed by applying a layer made of the resin composition of the present embodiment (hereinafter referred to as a high refractive index layer) on various substrates such as glass, plastic film, plastic sheet, etc. After curing by irradiation, a layer having a refractive index lower than that of the high refractive index layer (hereinafter referred to as a low refractive index layer) is formed on the high refractive index layer.
  • a layer made of the resin composition of the present embodiment hereinafter referred to as a high refractive index layer
  • a low refractive index layer a layer having a refractive index lower than that of the high refractive index layer
  • Base materials include glass base materials such as alkali-free glass, alkali glass, borosilicate glass, and quartz, ceramic base materials such as silica, alumina, and silicon nitride, and metals such as silicone, aluminum, stainless steel, iron, copper, and silver. From resins such as base materials, acrylic resins, styrene resins, carbonate resins, olefin resins, polyester resins, polyimide resins, polyamide resins, epoxy resins, silicone resins, fluorine resins, and cellulose resins A film base material, a sheet base material, or the like can be used.
  • Examples of the low refractive index layer include inorganic films and organic films.
  • Examples of the inorganic film include fluorides of alkali metals such as magnesium fluoride and potassium fluoride, silica, and the like.
  • Examples of the organic film include fluorine resins such as polyperfluoroethylene and perfluorocycloolefin, polyether resins such as polyethylene glycol, silicone resins, acrylic resins, epoxy resins, urethane resins, and fluorine-modified resins thereof. .
  • the resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, so a liquid crystal panel, an organic electroluminescence panel, a touch panel, a projector, a smartphone, a mobile phone, a digital camera, a digital movie display element, It can be used as various sensor parts such as CCD, CMOS, biochip, coating material for semiconductor elements such as flash memory, DRAM, semiconductor laser, and also as a high refractive index layer for antireflection film and optical waveguide film.
  • the resin composition having the above configuration has both a high refractive index and high transparency, an adhesive suitable for bonding optical components can be provided.
  • A Fluorene compound (A-1) 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd. “BPFEA”) (A-2) 9,9-bis [4- (2-acryloyloxydiethoxy) phenyl] fluorene (“Ocsol EA-0200” manufactured by Osaka Gas Chemical Company)
  • B (Meth) acrylate having an alicyclic hydrocarbon group (B-1) dicyclopentenyloxyethyl methacrylate (“Fancryl FA-512M” manufactured by Hitachi Chemical Co., Ltd., homopolymer Tg: 46 ° C.) (B-2) Cyclohexyl methacrylate (Kyoeisha Chemical Co., Ltd.
  • C Monofunctional (meth) acrylate having aromatic ring
  • C-1 Phenoxyethyl acrylate (“Light acrylate PO-A” manufactured by Kyoeisha Chemical Co., Ltd.)
  • C-2) Phenoxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester PO”)
  • C-3) Benzyl acrylate (Osaka Organic Chemical Co., Ltd. “Biscoat # 160”)
  • C-4 benzyl methacrylate (“Light Ester BZ” manufactured by Kyoeisha Chemical Co., Ltd.)
  • D Photoradical polymerization initiator (D-1) 1-hydroxy-cyclohexyl phenyl ketone (“IRGACURE 184” manufactured by BASF) (D-2) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure 819” manufactured by BASF) (D-3) Benzyldimethyl ketal (“Irgacure 651” manufactured by BASF)
  • E Silane coupling agent (E-1) ⁇ -methacryloyloxypropyltrimethoxysilane (“KBM-503” manufactured by Shin-Etsu Silicone) (E-2) Phenyltrimethoxysilane (“KBM-103” manufactured by Shin-Etsu Silicone) (E-3) Phenyltriethoxysilane (“KBE-103” manufactured by Shin-Etsu Silicone)
  • Examples 1 to 30, Comparative Examples 1 to 10 The raw materials of the types shown in Tables 1 to 4 were mixed in the content ratios (units are parts by mass) shown in Tables 1 to 4 to prepare a resin composition for a coating material, and the evaluation described below was performed. Various evaluation results are shown in Tables 1 to 4. Unless otherwise specified, the test was carried out in an environment of 23 ° C. and 50% humidity.
  • the refractive index was evaluated by measuring the refractive index at a temperature of 25 ° C. and a wavelength of 589 nm using a multiwavelength Abbe refractometer (“DR-M2” manufactured by Atago Co., Ltd.).
  • a cut line was placed in the cured film so as to be 2 mm long ⁇ 2 mm wide ⁇ 25 squares in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then cellophane.
  • a tape (model CT-405AP manufactured by Nichiban Co., Ltd .: width 24 mm, adhesive strength 23 N / 10 mm) was applied and 180 ° peeling was performed. The number of cells remaining after 180 ° peeling was counted and evaluated. Other conditions that were not specified were in accordance with JIS K 5600-5-6.
  • a resin composition is applied to a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, 25 mm ⁇ 25 mm ⁇ 2.0 mm) in a circular shape with a diameter of 8 mm and a film thickness of 80 ⁇ m, and then mounted on an ultra-high pressure mercury lamp.
  • a cured test piece was prepared with an apparatus (“UL-750” manufactured by HOYA) under conditions of an irradiation intensity of a wavelength of 365 nm of 30 mW / cm 2 and an integrated light amount of 3,000 mJ / cm 2 .
  • the produced test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min using a tensile tester in an environment of 23 ° C. and humidity 50% RH.
  • the resin compositions of Experimental Examples 1 to 30 had a high refractive index and high transparency, a short fixing time, and excellent adhesion and light resistance. Moreover, since this composition before hardening is low-viscosity, it was excellent in workability
  • the present invention has a high refractive index and high transparency, a short fixing time, and excellent adhesion and light resistance.
  • the present invention has a low viscosity and excellent workability.
  • the present invention is used for various sensor elements, display elements, optical components, and the like.
  • the present invention is used for surface protection of sensor elements, display elements, etc., and anti-reflection films, optical waveguide films, and adhesives for optical components.
  • the present invention is used for a high refractive index layer of an antireflection film or an optical waveguide film.
  • the present invention is used for an adhesive composition for optical parts used for bonding optical elements such as optical lenses, prisms, and optical waveguides.
  • the resin composition of the present invention is excellent in optical properties such as high transparency and high refractive index, display elements such as liquid crystal panels, organic electroluminescence panels, touch panels, projectors, smartphones, mobile phones, digital cameras, digital movies, Suitable for use as sensor elements for various sensor components such as CCD, CMOS, and biochip, coating materials used for semiconductor elements such as flash memory, DRAM, and semiconductor laser, and also as a high refractive index layer for antireflection films and optical waveguide films. be able to. Since the resin composition of this invention is excellent in adhesiveness and light resistance, it can be used suitably also as an adhesive agent for optical components. The present invention is very useful in industry.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

　La présente invention concerne une composition de résine photodurcissable à temps de prise court possédant un indice de réfraction élevé et une transparence élevée. Une composition de résine photodurcissable contient un composé fluorène spécifique en tant que constituant (A), un méthacrylate monofonctionnel possédant un groupe hydrocarbure alicyclique en tant que constituant (B), un méthacrylate monofonctionnel possédant un cycle aromatique en tant que constituant (C) et un initiateur de polymérisation photoradicalaire en tant que constituant (D), la teneur en constituant (A) étant de 10 à 70 parties en masse, la teneur en constituant (B) étant de 5 à 65 parties en masse et la teneur en constituant (C) étant de 5 à 65 parties en masse pour 100 parties totales en masse de constituants (A) à (C).
PCT/JP2014/064534 2014-05-30 2014-05-30 Composition de résine photodurcissable WO2015181984A1 (fr)

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PCT/JP2014/064534 WO2015181984A1 (fr) 2014-05-30 2014-05-30 Composition de résine photodurcissable
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CN114214022A (zh) * 2021-12-17 2022-03-22 Oppo广东移动通信有限公司 光固化胶、壳体和电子设备
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CN113527930B (zh) * 2020-04-20 2023-04-07 杭州光粒科技有限公司 光致聚合物组合物、光栅及其制备方法

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CN114585658A (zh) * 2019-10-29 2022-06-03 积水化学工业株式会社 电子器件用光固化性树脂组合物
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KR102206665B1 (ko) 2021-01-22

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