WO2017111064A1 - 光硬化性樹脂組成物、遮光用塗料、及び硬化物 - Google Patents

光硬化性樹脂組成物、遮光用塗料、及び硬化物 Download PDF

Info

Publication number
WO2017111064A1
WO2017111064A1 PCT/JP2016/088460 JP2016088460W WO2017111064A1 WO 2017111064 A1 WO2017111064 A1 WO 2017111064A1 JP 2016088460 W JP2016088460 W JP 2016088460W WO 2017111064 A1 WO2017111064 A1 WO 2017111064A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
resin composition
glass substrate
photocurable resin
Prior art date
Application number
PCT/JP2016/088460
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
高木　俊輔
藤井　徹也
健実 大久保
Original Assignee
日立化成株式会社
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 日立化成株式会社 filed Critical 日立化成株式会社
Priority to CN201680074808.1A priority Critical patent/CN108650887A/zh
Priority to KR1020187017080A priority patent/KR102642394B1/ko
Priority to JP2017558277A priority patent/JP6930425B2/ja
Publication of WO2017111064A1 publication Critical patent/WO2017111064A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Definitions

  • the present disclosure relates to a photocurable resin composition, a shading paint, a cured product, a glass substrate, a display device, and a mobile terminal.
  • the present disclosure also relates to a method for producing a cured product and a method for producing a light-shielded glass substrate.
  • cover glass In mobile terminals such as smartphones and tablets, screens are becoming larger and thinner for lightening. Accordingly, the cover glass used is also becoming thinner. Therefore, high-strength chemically strengthened glass is widely used for the cover glass.
  • the cover glass may crack at the end due to contact or impact during the manufacturing process. In chemically strengthened glass, the strength tends to decrease significantly due to cracks.
  • the present disclosure is capable of protecting the end portion of the glass base material, and can reduce light leakage from the end portion of the glass base material.
  • the present disclosure provides a glass substrate in which end portions are protected and light leakage is suppressed, and a display element and a portable terminal including the glass substrate.
  • the present disclosure provides a method for producing a cured product and a method for producing a light-shielded glass substrate.
  • the present invention includes various embodiments. Examples of embodiments are listed below. The present invention is not limited to the following embodiments.
  • One embodiment is used to protect at least a part of the edge of the glass substrate, and the transmittance of the peak wavelength of light irradiated for curing is 10% or more than the average transmittance of visible light.
  • the present invention relates to a high photocurable resin composition.
  • Another embodiment is used to protect at least a part of the edge of the glass substrate, and the transmittance of the peak wavelength of light irradiated for curing is 60% or more, and is visible.
  • the present invention relates to a photocurable resin composition having an average light transmittance of 50% or less.
  • Another embodiment is used to protect at least a part of the edge of the glass substrate, and contains at least a monomer having a polymerizable unsaturated group, an acrylic compound, and a colorant, and the coloring
  • the agent relates to a photocurable resin composition containing a colorant having a peak wavelength transmittance of light irradiated for curing of 10% or more higher than an average visible light transmittance.
  • Another embodiment is used to protect at least a part of the edge of the glass substrate, and contains at least a monomer having a polymerizable unsaturated group, an acrylic compound, and a colorant, and the coloring
  • the present invention relates to a photocurable resin composition comprising a colorant having a peak wavelength transmittance of light irradiated for curing of 60% or more and an average visible light transmittance of 50% or less. .
  • Another embodiment relates to a light-shielding paint using any one of the above-described photocurable resin compositions.
  • Another embodiment relates to a cured product obtained by curing any one of the above-described photo-curable resin compositions or the light-shielding paint.
  • Another embodiment relates to a glass substrate in which at least a part of the end portion is shielded from light by the cured product.
  • the photocurable resin composition or the photocurable paint is applied to at least a part of an end portion of a glass substrate to form a coating film
  • the present invention relates to a method for producing a light-shielded glass substrate, comprising a step of curing by irradiation to form a protective film.
  • a photocurable resin composition e.g., a photocurable resin composition, a light-shielding paint, and A cured product is provided.
  • the edge part is protected and the glass base material with which light leakage was prevented, a display element provided with this, and a portable terminal are provided.
  • cured material and the manufacturing method of the light-shielded glass substrate are provided.
  • FIG. 1A is a schematic plan view illustrating an example of a glass substrate according to an embodiment
  • FIG. 1B is a schematic cross-sectional view illustrating an example of a glass substrate according to an embodiment
  • FIG. 2A is a schematic plan view illustrating an example of a glass substrate according to an embodiment in which a cured product is provided on a side surface
  • FIGS. 2B and 2C are diagrams in which the cured product is provided on a side surface.
  • It is a cross-sectional schematic diagram which shows an example of the glass base material of one embodiment
  • FIG. 3 is a graph showing the transmittance of the colorant used in Example 1 and Comparative Example 1 with respect to light having a wavelength of 300 to 700 nm.
  • the present invention is not limited to the following embodiments.
  • the inventors can protect a glass substrate by using a paint having a specific light transmittance or a paint containing a colorant having a specific light transmittance, and reducing light leakage.
  • the present invention including various embodiments has been completed.
  • the photocurable resin composition is used to protect at least a part of the edge of the glass substrate, and the transmittance (hereinafter referred to as the peak wavelength of light irradiated for curing).
  • the composition is such that “irradiation light transmittance” and average visible light transmittance (hereinafter also referred to as “visible light transmittance”) are in a specific relationship or in a specific range.
  • the photocurable resin composition is used for protecting at least a part of the end portion of the glass substrate, and includes at least a monomer having a polymerizable unsaturated group, an acrylic compound. And a coloring agent, wherein the coloring agent has a specific relationship or a specific range with respect to the irradiation light transmittance and the visible light transmittance.
  • the photocurable resin composition can be preferably used as a material for protecting the glass substrate because it can be easily applied to the end of the glass substrate. However, if the photocurable resin composition is to have a light-shielding function, the photocuring of the composition becomes insufficient and the protection performance of the glass substrate is inferior. In an embodiment, in the photocurable resin composition, by defining the light transmittance of the composition and / or colorant, protection of the edge of the glass substrate and light leakage from the edge of the glass substrate are prevented. It is possible to achieve both prevention and prevention.
  • ultraviolet rays are preferably used.
  • the light source used is not particularly limited, and examples thereof include LED lamps, mercury lamps (low pressure, high pressure, ultrahigh pressure, etc.), metal halide lamps, excimer lamps, xenon lamps, etc., preferably LED lamps, mercury lamps, Metal halide lamps and the like.
  • the peak wavelength of light irradiated for curing refers to the wavelength at which the intensity is maximum for the light irradiated to the photocurable resin composition during curing.
  • the peak wavelength is, for example, 365 nm, 385 nm, or the like.
  • the measurement of the irradiation light transmittance of a photocurable resin composition is performed using the hardened
  • the photocurable resin composition is dropped on one surface and stretched with a glass rod to form a coating layer (thickness 150 ⁇ m).
  • the coating layer is irradiated with light and cured to obtain a cured product layer (thickness 150 ⁇ m).
  • the irradiation intensity and total irradiation amount at this time can be set to, for example, 150 mW / cm 2 and 1,000 mJ / cm 2 .
  • the irradiation light transmittance of the cured product layer (that is, the irradiation light transmittance of the laminate of the cured product layer and the glass substrate) is measured by visible ultraviolet spectroscopy. Measure using a photometer.
  • the transmittance of the cured layer is measured with respect to light having a wavelength of 365 nm.
  • the average visible light transmittance refers to the average transmittance of light having a wavelength of 400 to 700 nm.
  • the average visible light transmittance of the photocurable resin composition is performed by the following method using, for example, the cured product layer. In the same manner as described above, with the cured product layer formed on the glass substrate, the transmittance of the cured product layer (cured product layer and glass substrate and light with a wavelength of 400 to 700 nm at 1 nm intervals). The transmittance of the laminate is measured using a visible ultraviolet spectrophotometer. The average value of the obtained values is obtained and taken as the average visible light transmittance.
  • a glass substrate having a high light transmittance in the wavelength range of 300 to 700 nm is used.
  • the transmittance is preferably 75% or more, more preferably 80% or more, still more preferably 85% or more, particularly preferably 90% or more, and most preferably 95% or more over a wavelength range of 300 to 700 nm.
  • the photocurable resin composition preferably has an irradiation light transmittance of 10% or more higher than the visible light transmittance. If it is less than 10%, it may be difficult to achieve both end protection and light shielding. More preferably, it is 20% or more, and further preferably 30% or more. An upper limit is not specifically limited, The one where the difference of both is large is preferable. If the irradiation light transmittance is 10% or more higher than the visible light transmittance, the range of each transmittance is not particularly limited. In one embodiment, the photocurable resin composition preferably has an irradiation light transmittance of 60% or more and a visible light transmittance of 50% or less.
  • the irradiation light transmittance is less than 60% or the visible light transmittance exceeds 50%, it may be difficult to achieve both end protection and light shielding properties.
  • the irradiation light transmittance is more preferably 65% or more, and further preferably 70% or more.
  • the visible light transmittance is more preferably 45% or less, still more preferably 40% or less.
  • a material that absorbs less light for curing may be used as the material of the photocurable resin composition.
  • a colorant that has low absorption with respect to light irradiated for curing and high absorption with respect to visible light may be used as the colorant.
  • a particularly preferred photocurable resin composition has an irradiation light transmittance of 10% or more higher than the visible light transmittance, an irradiation light transmittance of 60% or more, and a visible light transmittance of 50% or less.
  • permeability of the light of wavelength 365nm is 10% or more higher than the average transmittance
  • the photocurable resin composition preferably has a light transmittance of wavelength of 365 nm of 60% or more and an average visible light transmittance of 50% or less.
  • the transmittance of light having a wavelength of 365 nm is more preferably 65% or more, and still more preferably 70% or more.
  • the visible light transmittance is more preferably 45% or less, still more preferably 40% or less.
  • the photocurable resin composition is preferably used for protecting at least a part of the end of the glass substrate.
  • ultraviolet rays are preferably used.
  • the wavelength of the ultraviolet light is not particularly limited, but is, for example, 365 nm.
  • the transmittance of light having a wavelength of 365 nm of the photocurable resin composition can also be measured by the same method as the irradiation light transmittance.
  • the photocurable resin composition preferably comprises (A) a monomer having a polymerizable unsaturated group (also referred to as “(A) monomer”), (B) an acrylic compound, And (E) a colorant.
  • the photocurable resin composition comprises (C) a phosphoric acid compound having a polymerizable unsaturated group (also referred to as “(C) phosphoric acid compound”) and / or (D) an optional component such as a photopolymerization initiator. Furthermore, you may contain.
  • the colorant preferably contains a colorant whose irradiation light transmittance is 10% or more higher than the visible light transmittance. If it is less than 10%, it may be difficult to achieve both end protection and light shielding.
  • the colorant preferably includes a colorant having an irradiation light transmittance of 60% or more and a visible light transmittance of 50% or less. If the irradiation light transmittance is less than 60% or the visible light transmittance exceeds 50%, it may be difficult to achieve both end protection and light shielding properties.
  • the measuring method of the light transmittance of a coloring agent is mentioned later.
  • the colorant preferably contains a colorant having a transmittance of light having a wavelength of 365 nm that is 10% or more higher than the average transmittance of visible light. Furthermore, in one example, the colorant (E) preferably contains a colorant having a transmittance of light of a wavelength of 365 nm of 60% or more and a visible light transmittance of 50% or less.
  • A) As the polymerizable unsaturated group possessed by the monomer for example, vinyl group (ethenyl group), ethynyl group, allyl group, (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group And groups having a carbon-carbon double bond such as
  • the monomer (A) preferably has a (meth) acryloyloxy group.
  • the monomer has at least one polymerizable unsaturated group in the molecule.
  • Examples of (A) monomers include (A-1) (meth) acrylic acid ester monomers, (A-2) (meth) acrylamide monomers, and the like.
  • (A) monomer a compound different from (B) acrylic compound and (C) phosphoric acid compound described later is used. Regarding the term “(meth)”, it is meant that (B) the acrylic compound and (C) the phosphoric acid compound also contain at least one.
  • Examples of the monofunctional (meth) acrylic acid ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, Butoxyethyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate , Undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate,
  • bifunctional (meth) acrylic acid ester monomer examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate.
  • trifunctional or higher functional (meth) acrylic acid ester monomers examples include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, Ethoxylated propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated propoxylated pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythrito
  • A-1) Monofunctional (meth) acrylic acid ester-based monomer from the viewpoints of compatibility with other components such as acrylic compounds and colorants, and hardness characteristics during curing Monomers, more preferably monofunctional alicyclic (meth) acrylates, and even more preferably isobornyl (meth) acrylate are used.
  • (Meth) acrylamide monomers include (meth) acrylamide, methyl (meth) acrylamide, dimethyl (meth) acrylamide, ethyl (meth) acrylamide, diethyl (meth) acrylamide, n-propyl (meth) acrylamide, di- n-propyl (meth) acrylamide, isopropyl (meth) acrylamide, diisopropyl (meth) acrylamide, n-butyl (meth) acrylamide, di-n-butyl (meth) acrylamide, isobutyl (meth) acrylamide, diisobutyl (meth) acrylamide, tert-butyl (meth) acrylamide, di-tert-butyl (meth) acrylamide, n-pentyl (meth) acrylamide, di-n-pentyl (meth) acrylamide, n-hexyl (meth) actyl Rua
  • (meth) acryloylmorpholine is preferably used from the viewpoints of compatibility with other components such as an acrylic compound and a colorant, and hardness characteristics upon curing.
  • (A) Monomers can be used singly or in combination of two or more. From the viewpoints of compatibility with other components such as an acrylic compound and a colorant, and hardness characteristics during curing, the monomer (A) is preferably used in combination of two or more types (A-1 ) Monomer and (A-2) monomer are more preferably used in combination. (A-1) Monofunctional (meth) acrylic acid ester monomer and (A-2) It is more preferable to use in combination with a monomer.
  • the content of the monomer is a photocurable resin from the viewpoints of viscosity characteristics, compatibility with other components such as acrylic compounds and colorants, handling properties, productivity, and hardness characteristics during curing. 10 mass% or more is preferable on the basis of the total mass of the composition, 30 mass% or more is more preferable, and 40 mass% or more is still more preferable.
  • the content of the monomer (A) is preferably 90% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less, based on the total mass of the photocurable resin composition. Is more preferable.
  • the acrylic compound is a compound having at least one (meth) acryloyl group or (meth) acryloyloxy group.
  • (meth) acrylate compounds having a urethane bond can be exemplified.
  • (B) As the acrylic compound a compound different from the phosphoric acid compound (C) described later is used.
  • Examples of (meth) acrylate compounds having a urethane bond include (meth) acrylic acid monomers having an OH group at the ⁇ -position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexa.
  • Reaction products with diisocyanate compounds such as methylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, PO-modified urethane di (meth) acrylate, EO and PO-modified urethane di ( Examples include meth) acrylate and carboxyl group-containing urethane (meth) acrylate.
  • a urethane oligomer is also preferably used as the (meth) acrylate compound having a urethane bond.
  • the weight average molecular weight of the acrylic compound is preferably 800 from the viewpoints of viscosity characteristics, compatibility with other components such as monomers and colorants, handling properties, productivity, and hardness characteristics upon curing. Above, more preferably 2,000 or more, still more preferably 4,000 or more. Further, the weight average molecular weight of the (A) acrylic compound is preferably 10,000 or less, more preferably 9,000 or less, and still more preferably 7,000 or less, from the same viewpoint. The weight average molecular weight is measured by gel permeation chromatography (GPC), and a value converted to standard polystyrene is used.
  • GPC gel permeation chromatography
  • Examples of commercially available products include “Art Resin UN-904” and “Art Resin UN-6060S” manufactured by Negami Kogyo Co., Ltd.
  • the content of the acrylic compound is a photocurable resin from the viewpoints of viscosity characteristics, compatibility with other components such as monomers and colorants, handling properties, productivity, and hardness characteristics during curing. 10 mass% or more is preferable on the basis of the total mass of the composition, 30 mass% or more is more preferable, and 40 mass% or more is still more preferable. Further, from the same viewpoint, the content of (B) the acrylic compound is preferably 90% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less, based on the total mass of the photocurable resin composition. Is more preferable.
  • the phosphoric acid compound is a compound having at least one selected from a phosphoric acid group and a phosphoric ester group and at least one polymerizable unsaturated group.
  • the polymerizable unsaturated group possessed by the phosphoric acid compound for example, vinyl group (ethenyl group), ethynyl group, allyl group, (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group And groups having a carbon-carbon double bond such as (C)
  • the phosphoric acid compound preferably has a (meth) acryloyloxy group.
  • the phosphoric acid compound is preferably ethylene oxide-modified phosphoric acid di (meth) acrylate and / or propylene oxide-modified phosphoric acid di (meth) acrylate, and is preferably ethylene oxide-modified phosphoric acid di (meth) acrylate. Is more preferable.
  • Examples of phosphoric acid compounds include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxybutyl (meth) acrylate, acid phosphooxypentyl (meth) acrylate, and acid phosphooxypoly Examples include compounds represented by the following formula (1) such as oxyethylene glycol monomethacrylate and acid phosphooxypolyoxypropylene glycol monomethacrylate.
  • R 1 represents hydrogen or a methyl group
  • R 2 represents a linear, branched or cyclic alkyl group
  • n represents a number of 1 or more
  • m represents a number of 1 to 3.
  • the number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 9, and still more preferably 1 to 6.
  • n is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3.
  • m is preferably 1 to 2, and more preferably 1.
  • Examples of (C) phosphoric acid compounds include 3-chloro-2-acid phosphooxypropyl (meth) acrylate, phenyl (2- (meth) acryloyloxyethyl) phosphate, diphenyl (2- (meth) acryloyloxyethyl). ) Phosphate, (meth) acryloyloxy-2-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, allyl alcohol acid phosphate Etc.
  • the phosphoric acid compound may be a salt such as a monomethanolamine salt or a monoethanolamine salt.
  • the phosphoric acid compound is preferably a compound represented by formula (1), more preferably, in formula (1), R 1 is a methyl group, R 2 is a dimethylene group or a pentamethylene group, and n In the formula (1), R 1 is a methyl group, R 2 is a dimethylene group, n is 1.5, and m is 1 It is a compound which is.
  • (C) Phosphoric acid compounds can be used singly or in combination of two or more.
  • the content of (C) phosphoric acid compound is 0.01 with respect to a total of 100 parts by mass of (A) monomer and (B) acrylic compound from the viewpoint of obtaining good adhesion to the glass substrate. More than mass part is preferable, 0.1 mass part or more is more preferable, and 0.3 mass part or more is still more preferable. Moreover, content of (C) phosphoric acid compound is 10 with respect to a total of 100 mass parts of (A) monomer and (B) acrylic compound from a viewpoint of maintaining stability of a photocurable resin composition. It is preferably no greater than 5 parts by mass, more preferably no greater than 5 parts by mass, and even more preferably no greater than 3 parts by mass.
  • Photopolymerization initiator (D) What is called a sensitizer is also contained in a photoinitiator.
  • the photopolymerization initiator include acridine; an acridine compound having at least one acridinyl group in the molecule; benzophenone; N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler's ketone), etc.
  • photopolymerization initiator can be used alone, or two or more types can be used in combination.
  • the content of the photopolymerization initiator is a total of (A) monomer and (B) acrylic compound from the viewpoint of sufficiently curing the surface of the photocurable resin composition and suppressing tackiness of the cured product. 0.1 mass part or more is preferable with respect to 100 mass parts, 1 mass part or more is more preferable, and 5 mass parts or more is still more preferable.
  • the content of the (D) photopolymerization initiator is based on a total of 100 parts by mass of the (A) monomer and the (B) acrylic compound from the viewpoint of obtaining sufficient curability and adhesion to the deep part. 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 12 parts by mass or less is still more preferable.
  • (E) Colorant for example, a coloring agent having a small absorption for light used for curing is used.
  • a coloring agent for example, a coloring agent having a small absorption for light used for curing is used.
  • a dye and a pigment are mentioned as a coloring agent, From a viewpoint of obtaining a uniform photocurable resin composition, Preferably a dye is used, More preferably, (A) Dye which melt
  • the dye is dissolved in the monomer (A).
  • a 50 mL beaker 10 mL of monomer (A) (temperature: 25 ° C.) is added, 10 mg of dye (solid mass) is added, and the mixture is stirred for 1 minute using a glass rod.
  • solid matter of the dye cannot be visually confirmed after stirring, it is determined that the dye is dissolved in the monomer (A).
  • the colorant (E) a colorant whose irradiation light transmittance is 10% or more higher than the visible light transmittance is used. More preferably, it is 20% or more, More preferably, it is 30% or more. An upper limit is not specifically limited, The one where the difference of both is large is preferable.
  • (E) a colorant having an irradiation light transmittance of 60% or more and a visible light transmittance of 50% or less is used as the colorant.
  • the irradiation light transmittance is more preferably 65% or more, and further preferably 70% or more.
  • the visible light transmittance is more preferably 45% or less, still more preferably 40% or less.
  • Particularly preferred (E) colorant has an irradiation light transmittance of 10% or more higher than the visible light transmittance, an irradiation light transmittance of 60% or more, and a visible light transmittance of 50% or less.
  • a colorant whose light transmittance at a wavelength of 365 nm is 10% or more higher than the average visible light transmittance is used. More preferably, it is 20% or more, and further preferably 30% or more.
  • a colorant having a transmittance of light having a wavelength of 365 nm of 60% or more and a visible light transmittance of 50% or less is used as the colorant (E).
  • the transmittance of light having a wavelength of 365 nm is more preferably 65% or more, and still more preferably 70% or more.
  • the visible light transmittance is more preferably 45% or less, still more preferably 40% or less.
  • the irradiation light transmittance of the colorant can be measured by the following method.
  • the transmittance at the peak wavelength of light irradiated for curing is measured with a visible ultraviolet spectrophotometer (for example, “UV-2400PC” manufactured by Shimadzu Corporation). The resolution wavelength is 1 nm and the measurement is performed in the range of 300 to 780 nm.
  • the transmittance of the colorant having a wavelength of 365 nm can also be measured by the same method as the irradiation light transmittance.
  • the average visible light transmittance refers to the average transmittance of light having a wavelength of 400 to 700 nm.
  • the average visible light transmittance can be measured by the following method. Using the colorant solution prepared in the same manner as described above, the transmittance is measured every 1 nm in the wavelength range of 400 to 700 nm with a spectrocolorimeter (for example, “CM-3700A” manufactured by Konica Minolta, Inc.). The average value of the obtained values is obtained and used as the average transmittance.
  • a spectrocolorimeter for example, “CM-3700A” manufactured by Konica Minolta, Inc.
  • (E) There is no particular limitation on the hue of the colorant.
  • colorants having various hues it is possible to prepare a photocurable resin composition that matches the hue of the hazel.
  • a black colorant such as a black dye is used.
  • Examples of the colorant include phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, aniline black, and perylene black.
  • Examples of commercially available products include “elixa Black850” manufactured by Orient Chemical Industries, Ltd. “Elexa Black850” has a transmittance of light of wavelength 365 nm higher than the average transmittance of visible light by 10% or more, a transmittance of light of wavelength 365 nm of 60% or more, and a visible light transmittance of The colorant is 50% or less.
  • the colorant can be used singly or in combination of two or more.
  • the content of the colorant is 0.1 parts by mass or more with respect to 100 parts by mass in total of the (A) monomer and the (B) acrylic compound. Preferably, 0.3 mass part or more is more preferable, and 0.5 mass part or more is still more preferable.
  • the content of (E) the colorant is the sum of (A) the monomer and (B) the acrylic compound from the viewpoint of curability of the photocurable resin composition, particularly from the viewpoint of sufficiently curing the deep part. 10 mass parts or less are preferable with respect to 100 mass parts, 5 mass parts or less are more preferable, and 3 mass parts or less are still more preferable.
  • the photocurable resin composition may contain various additives as necessary.
  • additives include adhesion improvers such as coupling agents, polymerization inhibitors, light stabilizers, antifoaming agents, fillers, antioxidants, chain transfer agents, thixotropy imparting agents, plasticizers, flame retardants, and mold release agents. Agents, surfactants, lubricants, antistatic agents and the like.
  • adhesion improvers such as coupling agents, polymerization inhibitors, light stabilizers, antifoaming agents, fillers, antioxidants, chain transfer agents, thixotropy imparting agents, plasticizers, flame retardants, and mold release agents.
  • Agents, surfactants, lubricants, antistatic agents and the like can be used as these additives.
  • An additive can be used individually by 1 type or in combination of 2 or more types.
  • titanate coupling agents for example, titanate coupling agents, silane coupling agents and the like can be used.
  • a titanate coupling agent a titanate coupling agent having an alkylate group having at least 1 to 60 carbon atoms, a titanate coupling agent having an alkyl phosphite group, a titanate coupling agent having an alkyl phosphate group, an alkyl pyrone Examples thereof include a titanate coupling agent having a phosphate group.
  • Silane coupling agents include amino silane coupling agents, ureido silane coupling agents, vinyl silane coupling agents, methacrylic silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, and isocyanates. And silane coupling agents.
  • polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butylcatechol, quinones such as 2,6-di-tert-butyl-4-methylphenol, and pyrogallol.
  • antifoaming agent examples include silicone oil, fluorine oil, and polycarboxylic acid polymer.
  • the photocurable resin composition comprises (A) a monomer, (B) an acrylic compound, and (E) a colorant, and (C) a phosphate compound, if necessary, ( D) It can manufacture by mixing a photoinitiator and / or an additive by stirring. Stirring may be performed by a known method using a stirring bar, a stirring blade, or the like.
  • the temperature at the time of stirring is preferably a temperature at which (E) the colorant can be sufficiently dissolved, and can be, for example, 60 to 90 ° C.
  • the light-shielding paint contains at least (A) a monomer, (B) an acrylic compound, and (E) a colorant, and (C) a phosphoric acid compound, (D) a photopolymerization initiator, and An additive may be contained.
  • One embodiment relates to a cured product obtained by curing the photocurable resin composition or the light-shielding coating material.
  • cured material is provided in at least one part of the edge part of a glass base material, and is used in order to light-shield visible light.
  • the average visible light transmittance of the cured product is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less.
  • the average visible light transmittance of the cured product is measured with respect to the maximum thickness t direction of the cured product, which will be described later, according to the measurement method for the photocurable resin composition described above.
  • the cured product can be obtained by a production method including a step of curing the photocurable resin composition or the photocurable paint by light irradiation.
  • the light source described above can be used for light irradiation.
  • ⁇ Glass substrate> One embodiment relates to a glass substrate in which at least a part of the end portion is shielded from light by the cured product.
  • the material of the glass substrate is not particularly limited. Examples of the glass include alkali-free glass, low alkali glass, alkali glass, and quartz glass. It may be a glass substrate chemically strengthened by an ion exchange method.
  • the size and thickness of the glass substrate are not particularly limited, and can be appropriately determined according to the application.
  • the size is about 60 mm ⁇ 120 mm and the thickness is about 0.55 mm.
  • the end portion of the glass substrate refers to a portion including at least the side surface of the glass substrate, and may be a portion including not only the side surface of the glass substrate but also the edge of one or both surfaces of the glass substrate.
  • FIG. 1A shows a schematic plan view of a glass substrate
  • FIG. 1B shows a schematic sectional view of the glass substrate.
  • 1 (a) and 1 (b) 1 represents a glass substrate
  • 2 represents a side surface of the glass substrate
  • 3 represents an end of the glass substrate.
  • the light shielding is performed by applying the photocurable resin composition or the light shielding coating material to the edge of the glass substrate, forming a coating layer, curing the coating layer by irradiating light, and Is performed by forming a cured product.
  • the coating method include a potting method, a dipping method, a spray method, and a roll coating method. You may use dispensers, such as a syringe-type dispenser and a jet-type dispenser, for application
  • Examples of the curing method include a method of irradiating ultraviolet rays using a LED lamp, a mercury lamp (low pressure, high pressure, ultrahigh pressure, etc.), a metal halide lamp, an excimer lamp, a xenon lamp or the like as a light source.
  • FIG. 2 shows a glass substrate provided with a cured product on the side surface.
  • 4 is a cured product.
  • the thickness of the cured product 4 may be uniform or non-uniform, and the maximum thickness t of the cured product 4 is not particularly limited. As an example, when the glass substrate is used for a mobile phone, the maximum thickness t of the cured product 4 is 300 to 400 ⁇ m.
  • cured material may be provided in all the edge parts of a glass base material, or may be provided in a part.
  • the light-shielded glass substrate is coated with the photocurable resin composition or the photocurable paint on at least a part of the end of the glass substrate to form a coating film, and the coating film, It can be obtained by a production method including a step of curing by light irradiation to form a cured product.
  • the above-described coating method can be used for coating, and the above-described light source can be used for light irradiation.
  • ⁇ Display device> One embodiment relates to a display device including the glass substrate.
  • a glass base material is used for the display part of a display apparatus.
  • the display device include a flat panel display (FPD). Specifically, a liquid crystal display (LCD), a plasma display panel (PDP), an organic electroluminescence panel (OELP), a field emission display (FED), a cathode ray.
  • FPD flat panel display
  • LCD liquid crystal display
  • PDP plasma display panel
  • OELP organic electroluminescence panel
  • FED field emission display
  • CRT cathode ray
  • electronic paper etc.
  • a mobile terminal including the glass substrate.
  • a glass base material is used for the display part of a portable terminal.
  • the portable terminal include a mobile phone, a smartphone, a personal computer, an electronic dictionary, a calculator, and a game machine.
  • Embodiments of the present invention will be specifically described with reference to examples. Embodiments of the present invention are not limited to the following examples.
  • Example 1 As component (A-1), 37.8 parts by mass of isobornyl acrylate, as component (A-2), 4.2 parts by mass of acryloylmorpholine, as component (B), a urethane acrylate compound (art resin “Negami Kogyo Co., Ltd.” UN-904 "29 parts by mass and” UN-6060S "29 parts by mass) 58 parts by mass, (C) component 0.5 parts by mass of ethylene oxide-modified phosphate dimethacrylate, (D) component (1-hydroxycyclohexyl) 10 parts by weight of phenylmethanone, and 0.8 parts by weight of Colorant 1 (“elixa Black850” manufactured by Orient Chemical Co., Ltd.) as the component (E) are stirred while heating at 60 ° C., and the photocurable resin composition 1 Got.
  • a urethane acrylate compound art resin “Negami Kogyo Co., Ltd.” UN-904 "29 parts by mass and” UN-6060S “
  • a photocurable resin composition 2 was obtained in the same manner as in Example 1 except that the colorant 1 was changed to the colorant 2 ("OLIOENT0101" manufactured by Orient Chemical Co., Ltd.).
  • a colorant solution was obtained by adding 0.1 parts by weight of a colorant to 100 parts by weight of the solvent. Using the obtained colorant solution, the transmittance was measured with a visible ultraviolet spectrophotometer (“UV-2400PC” manufactured by Shimadzu Corporation). The decomposition wavelength was 1 nm, and the transmittance at a wavelength of 365 nm was measured.
  • UV-2400PC visible ultraviolet spectrophotometer
  • the transmittance was measured every 1 nm in the wavelength range of 400 to 700 nm with a spectrocolorimeter (“CM-3700A” manufactured by Konica Minolta, Inc.). The average value of the obtained values was determined. The results are shown in Table 1 and FIG.
  • UV-2400PC visible ultraviolet spectrophotometer
  • the glass substrate prepared in the same manner as described above was cured using a visible ultraviolet spectrophotometer (“UV-2400PC” manufactured by Shimadzu Corporation) at 1 nm intervals with respect to light in the wavelength range of 400 to 700 nm.
  • UV-2400PC visible ultraviolet spectrophotometer
  • the transmittance of the layer was measured. The average value of the obtained values was 50% or less.
  • the photocurable resin composition was apply
  • ultraviolet irradiation device peak wavelength of 365 nm, 1,000 mJ / cm 2 subjected to curing of the photocurable resin composition was used to form a protective film (cured product).
  • the obtained glass substrate had improved resistance to contact and impact, and the protective film had a sufficient light leakage effect.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Plasma & Fusion (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Polymerisation Methods In General (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Surface Treatment Of Glass (AREA)
  • Paints Or Removers (AREA)
  • Telephone Set Structure (AREA)
  • Laminated Bodies (AREA)
PCT/JP2016/088460 2015-12-22 2016-12-22 光硬化性樹脂組成物、遮光用塗料、及び硬化物 WO2017111064A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201680074808.1A CN108650887A (zh) 2015-12-22 2016-12-22 光固化性树脂组合物、遮光用涂料及固化物
KR1020187017080A KR102642394B1 (ko) 2015-12-22 2016-12-22 광경화성 수지 조성물, 차광용 도료, 및 경화물
JP2017558277A JP6930425B2 (ja) 2015-12-22 2016-12-22 光硬化性樹脂組成物、遮光用塗料、及び硬化物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-250109 2015-12-22
JP2015250109 2015-12-22

Publications (1)

Publication Number Publication Date
WO2017111064A1 true WO2017111064A1 (ja) 2017-06-29

Family

ID=59090517

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/088460 WO2017111064A1 (ja) 2015-12-22 2016-12-22 光硬化性樹脂組成物、遮光用塗料、及び硬化物

Country Status (5)

Country Link
JP (1) JP6930425B2 (ko)
KR (1) KR102642394B1 (ko)
CN (1) CN108650887A (ko)
TW (1) TWI782900B (ko)
WO (1) WO2017111064A1 (ko)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022508606A (ja) * 2018-10-08 2022-01-19 ジョンソン・アンド・ジョンソン・ビジョン・ケア・インコーポレイテッド 多波長レンズ形成システム及び方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110678487B (zh) * 2017-03-31 2021-10-15 昭和电工材料株式会社 固化性树脂组合物、玻璃构件、显示装置和便携终端

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005292801A (ja) * 2004-03-09 2005-10-20 Sekisui Chem Co Ltd 液晶表示素子用遮光シール剤、上下導通材料、及び、液晶表示素子
JP2015129074A (ja) * 2014-01-09 2015-07-16 昭和電工株式会社 ガラス端面補強用組成物、ガラス板材、ガラス板材の製造方法
WO2015146878A1 (ja) * 2014-03-26 2015-10-01 積水化学工業株式会社 光湿気硬化型樹脂組成物、電子部品用接着剤、及び、表示素子用接着剤
JP2015200775A (ja) * 2014-04-08 2015-11-12 東洋インキＳｃホールディングス株式会社 黒色組成物、黒色塗膜、および積層体
JP2015202429A (ja) * 2014-04-11 2015-11-16 Jsr株式会社 基板エッジ保護層の形成方法
JP2015205784A (ja) * 2014-04-17 2015-11-19 旭硝子株式会社 粘着層付きカバーガラス

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4011811B2 (ja) * 2000-01-14 2007-11-21 Ｊｓｒ株式会社 光硬化性樹脂組成物及び光学部材
JP2007245622A (ja) * 2006-03-17 2007-09-27 Toppan Printing Co Ltd ハードコート層用組成物及び積層体
CN102478727B (zh) 2010-11-28 2016-04-06 宸鸿科技(厦门)有限公司 触控显示装置的制造方法与显示装置、触控显示装置
JP2014056222A (ja) * 2012-09-14 2014-03-27 Japan Display Inc 表示装置及びカバー部材
WO2014188850A1 (ja) * 2013-05-21 2014-11-27 昭和電工株式会社 遮光性防湿絶縁塗料、遮光性防湿絶縁塗料を用いた封止・絶縁処理方法、および遮光性防湿絶縁塗料によって封止・絶縁処理された電子部品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005292801A (ja) * 2004-03-09 2005-10-20 Sekisui Chem Co Ltd 液晶表示素子用遮光シール剤、上下導通材料、及び、液晶表示素子
JP2015129074A (ja) * 2014-01-09 2015-07-16 昭和電工株式会社 ガラス端面補強用組成物、ガラス板材、ガラス板材の製造方法
WO2015146878A1 (ja) * 2014-03-26 2015-10-01 積水化学工業株式会社 光湿気硬化型樹脂組成物、電子部品用接着剤、及び、表示素子用接着剤
JP2015200775A (ja) * 2014-04-08 2015-11-12 東洋インキＳｃホールディングス株式会社 黒色組成物、黒色塗膜、および積層体
JP2015202429A (ja) * 2014-04-11 2015-11-16 Jsr株式会社 基板エッジ保護層の形成方法
JP2015205784A (ja) * 2014-04-17 2015-11-19 旭硝子株式会社 粘着層付きカバーガラス

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022508606A (ja) * 2018-10-08 2022-01-19 ジョンソン・アンド・ジョンソン・ビジョン・ケア・インコーポレイテッド 多波長レンズ形成システム及び方法

Also Published As

Publication number Publication date
JPWO2017111064A1 (ja) 2018-10-11
TWI782900B (zh) 2022-11-11
KR20180096624A (ko) 2018-08-29
KR102642394B1 (ko) 2024-02-28
TW201731978A (zh) 2017-09-16
CN108650887A (zh) 2018-10-12
JP6930425B2 (ja) 2021-09-01

Similar Documents

Publication Publication Date Title
JP6822515B2 (ja) 光硬化性樹脂組成物並びにそれを用いた光硬化性遮光塗料、光漏洩防止材、液晶表示パネル及び液晶表示装置、並びに光硬化方法
JP6095104B2 (ja) 活性エネルギー線硬化型樹脂組成物、表示素子用着色スペーサー及びブラックマトリックス
JP6643574B2 (ja) 光硬化性樹脂組成物
WO2017111064A1 (ja) 光硬化性樹脂組成物、遮光用塗料、及び硬化物
JP6075763B2 (ja) 活性エネルギー線硬化型樹脂組成物、及びそれを用いた表示素子用着色スペーサー及び／またはブラックマトリックス
JP5935337B2 (ja) 液状光硬化性樹脂組成物、光学部材、画像表示用装置及びその製造方法
TW201816053A (zh) 硬化性樹脂組成物、圖像顯示裝置及圖像顯示裝置的製造方法
JP6833211B2 (ja) インプリント成型用光硬化性樹脂組成物
JP7001051B2 (ja) 光硬化性樹脂組成物、光硬化性塗料、及び硬化物
JP6476660B2 (ja) 光硬化性樹脂組成物およびそれを用いた光硬化性遮光塗料、液晶表示パネル、液晶表示装置
KR102275382B1 (ko) 경화성 수지 조성물, 유리 부재, 표시 장치 및 휴대 단말기
JP2013221034A (ja) 紫外線硬化型光学樹脂接着剤組成物およびそれを用いた画像表示装置、並びに画像表示装置の製法
JP2018173486A (ja) 接合体、接合体の製造方法、液晶ディスプレイ及び画像表示装置
JP6835160B2 (ja) ガラス板保護用樹脂
JP2016117870A (ja) 光硬化性樹脂組成物及びそれを用いたガラス板保護用樹脂
JP6953687B2 (ja) 光硬化性防湿絶縁塗料及び電子部品の製造方法
EP4332123A1 (en) Cured film and display device
JP2018116271A (ja) 感光性樹脂組成物
WO2019064385A1 (ja) 硬化性樹脂組成物、画像表示装置及び画像表示装置の製造方法
TW201815580A (zh) 圖像顯示裝置的製造方法
JPWO2015080146A1 (ja) 活性エネルギー線硬化型樹脂組成物、及びそれを用いた表示素子用スペーサー及び／またはカラーフィルター保護膜
JP2013227419A (ja) 紫外線硬化型光学樹脂接着剤組成物およびそれを用いた画像表示装置、並びに画像表示装置の製法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16878950

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017558277

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20187017080

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16878950

Country of ref document: EP

Kind code of ref document: A1