WO2010146801A1 - Composé de (méth)acrylate d'uréthanne et composition de résine le contenant - Google Patents

Composé de (méth)acrylate d'uréthanne et composition de résine le contenant Download PDF

Info

Publication number
WO2010146801A1
WO2010146801A1 PCT/JP2010/003830 JP2010003830W WO2010146801A1 WO 2010146801 A1 WO2010146801 A1 WO 2010146801A1 JP 2010003830 W JP2010003830 W JP 2010003830W WO 2010146801 A1 WO2010146801 A1 WO 2010146801A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
compound
urethane
mixture
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2010/003830
Other languages
English (en)
Japanese (ja)
Inventor
小木聡
栗橋透
小淵香津美
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=43356135&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2010146801(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to KR1020117028584A priority Critical patent/KR101664003B1/ko
Priority to JP2011519522A priority patent/JP5757664B2/ja
Priority to CN201080026345.4A priority patent/CN102803332B/zh
Publication of WO2010146801A1 publication Critical patent/WO2010146801A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention includes at least two selected from the group consisting of dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
  • the present invention relates to a resin composition containing an acrylate compound (A) and a photopolymerization initiator, and a cured film of the resin composition. And since the cured film of the resin composition of the present invention is excellent in hardness, adhesion to a substrate, scratch resistance, etc., curl is small and cracks are less likely to occur, it can be used as a hard coat for plastic films and small casings. Useful.
  • the cured film of the resin composition of the present invention has good adhesion to the substrate, has high hardness, and has an appropriate flexibility, so that the resin composition of the present invention is a color filter (for example, Color filters used in color liquid crystal displays, color video cameras, color digital cameras, electronic papers, etc.), black matrixes, or spacers can also be used.
  • a color filter for example, Color filters used in color liquid crystal displays, color video cameras, color digital cameras, electronic papers, etc.
  • black matrixes, or spacers can also be used.
  • plastics that are excellent in various properties such as processability, transparency, and optical properties are used in the industry.
  • plastics are softer than glass and have defects such as the surface being easily scratched, it is common practice to coat a hard coating agent on the plastic surface.
  • the hard coat agent many thermosetting types such as silicone paints, acrylic paints, and melamine paints are known.
  • silicone hard coat agents have been mainly used because of their excellent performance and quality.
  • the silicone-based hard coat agent has a drawback that it has a long curing time and is expensive.
  • a photosensitive acrylic hard coat agent has been developed and used as a hard coat agent that compensates for the disadvantages of silicone hard coat agents (see Patent Document 1).
  • Acrylic hard coat agents are cured immediately upon irradiation with radiation such as ultraviolet rays, so that the processing speed is high, the hardness and the scratch resistance are excellent, and the cost is low. Therefore, at present, the acrylic hard coat agent has become the mainstream in the hard coat field.
  • the acrylic hard coat agent is suitable for coating the surface of the substrate during continuous processing of a substrate film such as polyester.
  • plastic base film examples include a polyester film, an acrylic film, a polycarbonate film, a vinyl chloride film, a triacetyl cellulose film, and a polyethersulfone film.
  • polyester films are most widely used because of various excellent properties. This polyester film is used for applications such as glass shatterproof film, automobile light-shielding film, whiteboard surface film, system kitchen surface antifouling film, and electronic materials. CRT flat TV, touch panel, liquid crystal display (LCD) ), A functional film in plasma display (PDP), organic EL display and the like.
  • electronic device cases such as home appliance bodies and switches, mobile phones, personal computers, and MP3 players are widely used as polyester resin moldings. All of these are hard-coated to prevent the surface from being scratched.
  • a hard-coated sheet or substrate such as polycarbonate or acrylic is used for an optical disk or a liquid crystal related member around a backlight.
  • Patent Document 3 attempts to improve hardness by adding polyfunctional urethane acrylate to the resin composition.
  • polyfunctional urethane acrylate there is a problem that the curing shrinkage of the polyfunctional urethane acrylate being used is large and cracks are observed.
  • Patent Document 4 polyfunctional urethane (meth) acrylate is used in a resin composition for hard coating of an antireflection material.
  • This hard coat is quite excellent in terms of hardness, curl resistance, scratch resistance, etc., but it is not always satisfactory and further improvements are desired.
  • the present inventors arrived at the present invention as a result of intensive studies to solve the above problems.
  • the present invention relates to the following inventions.
  • the polyisocyanate compound (b) of (II) is a diisocyanate compound alone or a combination of a diisocyanate compound and a triisocyanate compound, and the ratio of the diisocyanate compound to the triisocyanate compound is 1 mol of the diisocyanate compound.
  • X is an isocyanate residue
  • n is an integer of 0 to 100
  • Y is an organic group represented by the following general formula (2), wherein a, b and c are integers of 1 ⁇ a ⁇ 4, 0 ⁇ b ⁇ 3 and 0 ⁇ c ⁇ 3, respectively.
  • a + b + c 4
  • the mixture (a) in (I) contains 35 dipentaerythritol penta (meth) acrylate in the area ratio (%) of high performance liquid chromatography (HPLC) with respect to the total amount of the mixture (a).
  • the total of the three components including 90% to 100%, dipentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate added thereto is 90 to 100%, and the remaining 0 to 10% is dipentaerythritol tri (meta)
  • the urethane (meth) acrylate compound (A) according to any one of the above (1) to (4), (6) or (10), which is a multimeric acrylate of acrylate and tripentaerythritol.
  • the urethane (meth) acrylate compound (A) according to the above (13) or (14), wherein the diisocyanate compound is hexamethylene diisocyanate.
  • the mixture (a) is a ternary mixture of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, or dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol penta (4) A mixture of acrylate and dipentaerythritol hexaacrylate, wherein the polyisocyanate compound (b) is hexamethylene diisocyanate alone or both hexamethylene diisocyanate and hexamethylene diisocyanate trimer.
  • a cured film having high transparency, hardness and scratch resistance, hardly causing curling and cracking, or high transparency, suitable hardness and Provided are a resin composition that provides a cured film having flexibility and toughness, a cured product of the resin composition, a hard coat agent comprising the resin composition, and a hard coat using the same.
  • the hydroxyl value of the dipentaerythritol polyacrylate mixture (a ′) ⁇ containing is in the range of 80 to 120 mg KOH / g.
  • the desired urethane (meth) acrylate compound (A) ⁇ preferably urethane acrylate compound (A ') ⁇ can be efficiently obtained. it can.
  • a hard coat having high hardness, excellent curl resistance and high flexibility can be obtained.
  • the compound which does not contain skeleton derived from glycerol is a urethane (meth) acrylate compound (A1).
  • dipentaerythritol poly (meth) acrylate mixture (a) (hereinafter also simply referred to as poly (meth) acrylate mixture (a) or the mixture (a)) used as the raw material dehydrates dipentaerythritol and (meth) acrylic acid. It can be obtained by subjecting dipentaerythritol to (meth) acrylate by dehydration condensation reaction in the presence of a condensation catalyst such as an acid catalyst.
  • the mixture (a) is preferably selected from the group consisting of dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. At least three, more preferably three of dipentaerythritol tetra, penta and hexa (meth) acrylate.
  • the mixture (a) is a mixture containing four kinds of dipentaerythritol tri, tetra, penta and hexa (meth) acrylate, or a mixture containing three kinds of dipentaerythritol tetra, penta and hexa (meth) acrylate. is there.
  • the mixture (a) may further contain a trimeric or higher pentaerythritol acrylate such as tripentaerythritol by-produced during the condensation reaction.
  • acrylated products of dipentaerythritol acrylated products (dipentaerythritol tri, tetra, penta, and hexaacrylate) are more preferable than methacrylated products from the viewpoint of cost.
  • the content rate of each component with respect to the total amount of this mixture (a) is an area ratio (%) of a high performance liquid chromatography (HPLC), and is as follows.
  • Dipentaerythritol penta (meth) acrylate preferably dipentaerythritol pentaacrylate
  • a total of 85 of dipentaerythritol penta (meth) acrylate (preferably dipentaerythritol pentaacrylate) plus dipentaerythritol tetra and hexa (meth) acrylate (preferably dipentaerythritol tetra and hexaacrylate) is 85.
  • the three parties of the total 85 to 98% Ru preferably 90 to 97% der.
  • the remainder contains dipentaerythritol tri (meth) acrylate (preferably dipentaerythritol triacrylate) and / or a multimeric acrylate of the pentaerythritol trimer or more.
  • the contents of dipentaerythritol tetra and hexa (meth) acrylate are about 1 to 40% (preferably about 10 to 30%) and about 15 to 40% (preferably 20 to 20%), respectively.
  • the content of dipentaerythritol tri (meth) acrylate is about 0 to 10%, preferably 5% or less (including zero).
  • the multimeric acrylate may be included.
  • the manufacturing method of the said mixture (a) is demonstrated in detail below. As long as the said mixture (a) used as a raw material by this invention is obtained, it is not restricted to this.
  • Examples of the acid catalyst used in the above dehydration condensation reaction include mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid and trifluoromethanesulfonic acid, and fluorine.
  • Examples thereof include Lewis acids such as boron ether diethyl etherate and acid ion exchange resins. These acid catalysts may be used alone or in admixture of two or more.
  • sulfuric acid can be mentioned as a preferable acid catalyst.
  • the amount of the acid catalyst used is 0.01 to 50 mol%, preferably 0.1 to 20 mol%, relative to 1 mol of dipentaerythritol.
  • (meth) acrylic acid is used in an amount of 0.1 to 20 mol, preferably 1 to 10 mol, per 1 mol of dipentaerythritol.
  • the reaction time in the dehydration condensation reaction may be in the range of 1 to 24 hours, and the reaction temperature may be in the range of 60 to 150 ° C., but is 75 to 120 ° C., more preferably 100 to 120 ° C. from the viewpoint of shortening the reaction time and preventing polymerization. Is preferred.
  • an azeotropic solvent capable of distilling off water generated in the reaction is preferable.
  • the azeotropic solvent here, a solvent having a boiling point of 60 to 130 ° C., azeotropic with water, and easily separable from water is preferable.
  • the amount used is arbitrary, but is preferably 10 to 70% by mass with respect to the reaction mixture.
  • a commercially available (meth) acrylic acid used as a raw material is already added with a polymerization inhibitor such as 4-methoxyphenol, but a polymerization inhibitor may be added again during the reaction.
  • polymerization inhibitors include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, Examples include phenothiazine.
  • cupric chloride etc. can also be used. The amount used is 0.01 to 1% by mass with respect to the reaction mixture.
  • the urethane (meth) acrylate compound (A) of the present invention is (I) The following (i), (ii) or (iii), (I) including at least two selected from the group consisting of dipentaerythritol tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Dipentaerythritol poly (meth) acrylate mixture (a) (hereinafter referred to as the mixture (a)) having a hydroxyl value of 80 to 120 mgKOH / g, or (Ii) both the mixture (a) and glycerin, or (Iii) the mixture (a), glycerol and (meth) acrylates of C2-C5 aliphatic poly (2-4) ol, (Hereinafter also referred to
  • Any polyisocyanate compound (b) used for the production of the urethane (meth) acrylate compound (A) of the present invention can be used as long as it is a compound containing two or more isocyanate groups in one molecule. It is essential to contain a diisocyanate compound.
  • the polyisocyanate compound (b) is preferably a diisocyanate compound alone or a combination of a diisocyanate compound and another polyisocyanate. In the case of the combined use, the combined use of a diisocyanate compound and a triisocyanate compound is particularly preferable.
  • Examples of the polyisocyanate compound (b) that can be used in the present invention include aliphatic polyisocyanate compounds and aromatic type compounds.
  • polyisocyanate compounds examples thereof include polyisocyanate compounds, alicyclic polyisocyanates, trimer or multimer compounds thereof, burette type polyisocyanates, and allophanate type polyisocyanates.
  • a trimer or multimeric compound means a compound in which three isocyanate groups form one or more isocyanurate ring structures.
  • the polyisocyanate compound (b) used in the present invention may be a diisocyanate compound alone as described above, or may be a combination of a diisocyanate compound and another polyisocyanate compound.
  • any of them may be one kind or plural kinds. Usually, one type is preferable for each.
  • aliphatic polyisocyanate compound examples include hexamethylene diisocyanate (1,6-hexamethylene diisocyanate), isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and 1,3-diisocyanate cyclohexane.
  • a diisocyanate compound alone or a combination of a diisocyanate compound and a triisocyanate compound is preferable.
  • the ratio of the diisocyanate compound and the other polyisocyanate compound, preferably the triisocyanate compound is such that the other polyisocyanate compound (preferably the triisocyanate compound) is 0 to 10 mol, preferably 0 to 7 mol, per 1 mol of the diisocyanate compound. More preferably, it is 0 to 5 mol, and still more preferably about 0 to 3 mol.
  • diisocyanate compounds aliphatic diisocyanates are preferred, and C4 to C12 aliphatic diisocyanates are more preferred. Hexamethylene diisocyanate is most preferred, and among the triisocyanate compounds, hexamethylene diisocyanate trimer is preferred.
  • the use ratio of the polyisocyanate compound (b) to the mixture (a) is equivalent to an isocyanate group equivalent to 1 equivalent of active hydrogen groups in the mixture (a) (the dipentaerythritol poly (meth) acrylate mixture (a)).
  • glycerin is usually in the range of 0.01 to 10 equivalents as active hydrogen group equivalent to 1 equivalent of active hydrogen group in the poly (meth) acrylate mixture (a). It is in the range of 1 to 1 equivalent.
  • the active hydrogen group in the mixture (a) means a hydrogen atom in the hydroxy group
  • the active hydrogen groups in the (meth) acrylates of glycerin and C2 to C5 aliphatic poly (2 to 4) ol are respectively
  • the hydrogen atom in the hydroxy group in the compound of this is meant.
  • the term “hydroxyl equivalent” is also used, but it is used in the same meaning as the active hydrogen group equivalent.
  • the ratio of the polyisocyanate compound (b) to 1 mol of the mixture (a) is such that the hydroxyl group equivalent of the mixture (a), the isocyanate group equivalent in the polyisocyanate compound (b), glycerin and C2 to C5 fat
  • the polyisocyanate compound (b) can be added in an amount of 0.3 mol per 1 mol of the mixture (a). It is preferable to use within the range of about ⁇ 1 mol, preferably about 0.3 to 0.9 mol, more preferably 0.33 to 0.8 mol.
  • the polyisocyanate compound (b) is about 0.3 mol to 0.7 mol with respect to 1 mol of the mixture (a), Preferably about 0.33 mol to 0.6 mol is used.
  • the polyisocyanate compound (b) is further added according to the number of moles of glycerin used together. It is preferable to increase the amount used.
  • the amount of the polyisocyanate compound (b) to be increased is preferably in the range of about half to 1 times the number of moles of glycerin used.
  • the polyisocyanate compound (b) (preferably The amount of diisocyanate compound alone or a combination of diisocyanate compound and triisocyanate compound) is about 0 to 0.3 mol, more preferably about 0 to 0.2 mol, per 1 mol of the mixture (a). It is a ratio.
  • the polyisocyanate compound (b) is increased so that the equivalent number of NCO corresponding to the equivalent number of the hydroxyl group is obtained. It is preferable to do this.
  • the total equivalent number of active hydrogen groups of each component in the mixture (a) is the same as the NCO equivalent number of the polyisocyanate compound (b) to be reacted, or the NCO equivalent number is within 0.1%. It is preferable to react in an excessive amount.
  • 1 mole of the mixture (a) is the content ratio (number of moles) of each component in the mixture (a) to the total amount of the mixture (a) (sum of the number of moles of each component). It is a value when the sum of values calculated by multiplying the respective molecular weights is defined as the molecular weight of the mixture (a).
  • the (meth) acrylate of the C2-C5 aliphatic poly (2-4) ol used in (iii) of (I) includes C2-C5 aliphatic poly (2) such as ethylene glycol, propylene glycol and pentaerythritol. 4) (Meth) acrylate obtained by reaction of ol with (meth) acrylic acid can be mentioned.
  • the (meth) acrylate preferably contains 30 to 100% by mass, preferably 50 to 100% by mass of the (meth) acrylate having a hydroxyl group with respect to the total amount of the (meth) acrylate (the remainder being a hydroxyl group) Acrylate of C2-C5 aliphatic poly (2-4) ol).
  • hydroxyethyl (meth) acrylate poly (2-4) (meth) acrylate of pentaerythritol (preferably, a mixture of pentaerythritol di- or tri (meth) acrylate and pentaerythritol tetra (meth) acrylate),
  • the reaction of the component (I) containing the mixture (a) and the polyisocyanate (b) of (II) can be carried out in the same manner as in a normal urethanization reaction.
  • the reaction may be performed in the presence of an inert organic solvent, for example, a ketone solvent such as butanone and a catalyst, if necessary.
  • the reaction temperature is usually in the range of 30 to 150 ° C., preferably 50 to 100 ° C.
  • the end point of the reaction was calculated by a method in which the residual isocyanate group (NCO) content was reacted with excess n-butylamine and back titrated with 1N hydrochloric acid, and the residual isocyanate group (NCO) content was determined based on the polyisocyanate (b ) Is 0.5% or less, preferably 0.1% or less, based on the isocyanate group (NCO) content.
  • the acidic catalyst examples include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, titanium tetrabutoxide, zirconium tetrabutoxide, and other metal alkoxides, aluminum chloride and other Lewis acids, and 2-ethylhexanoic acid tin.
  • Tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate.
  • An acidic catalyst of a tin compound is preferable, and dibutyltin dilaurate is more preferable.
  • the addition amount of these catalysts is 0.1 mass part or more normally 1 mass part or less with respect to 100 mass parts of polyisocyanate compounds (b).
  • the urethane (meth) acrylate compound (A) obtained as described above is obtained not as a single urethane compound but as a mixture of urethane compounds having different degrees of polymerization and the like, like a polymer compound.
  • the poly (meth) acrylate mixture (a) is reacted with the polyisocyanate compound (b) in the presence of glycerin and (meth) acrylate of C2 to C5 aliphatic poly (2 to 4) ol.
  • This product becomes a complex polycondensate mixture (urethane (meth) acrylate compound).
  • the resulting urethane (meth) acrylate compound (A) has a viscosity (60 ° C.) of about 5 to 40 Pa ⁇ s, preferably about 10 to 38 Pa ⁇ s, more preferably about 12 to 38 Pa ⁇ s, and most preferably 14 to It is about 35 Pa ⁇ s. Further, among the most preferable, the curling property is less when the viscosity is 15 Pa ⁇ s or more, the curling property is further less when the viscosity is 17 Pa ⁇ s or more, and the curling property is the least when 18 Pa ⁇ s or more.
  • the weight average molecular weight (Mw) is about 3,000 to 50,000, preferably about 4,000 to 35,000, more preferably about 4,500 to 35,000, and still more preferably 5,000 to 35,000. About 000. In order to obtain a cured film with less curl, the weight average molecular weight is about 7,000 to 50,000, preferably about 7,000 to 35,000.
  • the number average molecular weight is about 1,400 to 2,500, preferably about 1,500 to 2,300, more preferably about 1,600 to 2,300, and still more preferably about 1,700 to 2,300. Most preferably, it is about 1,700 to 2,100.
  • One of the more preferred embodiments of the urethane (meth) acrylate compound (A) is that the weight average molecular weight is about 4,500 to 35,000, the number average molecular weight is about 1,500 to 2,300, and the viscosity (60 ° C.) is. 5 to 40 Pa ⁇ s. Further, in a more preferred embodiment, the weight average molecular weight is about 7,000 to 35,000, the number average molecular weight is about 1,700 to 2,300, and the viscosity (60 ° C.) is about 12 to 35 Pa ⁇ s. It is.
  • the urethane (meth) acrylate compound of the present invention is usually a urethane-modified (meth) acrylate (urethane (meth) acrylate) at a ratio calculated from the area ratio of HPLC and GPC (gel permeation chromatography). Is about 60 to 90%, preferably about 60 to 85%, and the remainder is about 10 to 40%, preferably about 15 to 40%, of non-urethane (meth) acrylate (unreacted diester derived from raw materials). It contains pentaerythritol hexa (meth) acrylate and non-urethaneized pentaerythritol multimers (multimers of tri or higher).
  • X represents an isocyanate residue
  • n represents an integer of 0 to 100
  • A, B, and Y represent an organic group represented by the following general formula (2).
  • the general formula (2) is a divalent group, and in the case of A and when B is present at the terminal, each independently The general formula (2) is a monovalent group.
  • the formula (2) can be represented by the following formula (2a).
  • the resin composition of the present invention contains the urethane (meth) acrylate compound (A) of the present invention and a photopolymerization initiator (C), and if necessary, (meth) acrylate (B), a curing accelerator. (D), diluent (E), and other components may be contained. Examples of other components include a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, and a crosslinking agent.
  • the resin composition of the present invention is a photosensitive resin composition and can be cured by irradiating energy rays such as ultraviolet rays.
  • the resin composition of this invention contains the organic solvent as a diluent (E) so that it can be easily made into film
  • the content of the urethane (meth) acrylate compound (A) of the present invention is usually 5 to 97% by mass when the solid content of the resin composition of the present invention is 100% by mass,
  • the amount is preferably 20 to 80% by mass, and in some cases, preferably about 40 to 95% by mass, more preferably about 50 to 95% by mass, and more preferably about 70 to 95% by mass.
  • the content of the urethane (meth) acrylate compound (A) with respect to the total amount of the resin composition of the present invention is usually 5 to 97% by mass, preferably about 20 to 95% by mass, and more preferably 40 to 95%. It is about mass%, more preferably about 45 to 95%.
  • Examples of the (meth) acrylate (B) that can be used in the present invention include (meth) acrylate compounds other than the urethane (meth) acrylate compound (A).
  • (meth) acrylate compounds other than the urethane (meth) acrylate compound (A) For example, mono (meth) acrylate (acrylate having one acryloyl group) or polyacrylate (bifunctional (meth) acrylate or trifunctional or higher (meth) acrylate: acrylate having two or more acryloyl groups) It is.
  • polyacrylate examples include polyester (meth) acrylate, urethane (meth) acrylate oligomer (excluding the urethane (meth) acrylate compound (A)), polyester (meth) acrylate oligomer, and epoxy (meth) acrylate oligomer. Including. You may use these individually or in mixture of 2 or more types. In the present invention, a poly (meth) acrylate compound having 2 to 6 (meth) acryloyl groups is preferred.
  • expressions such as “(meth) acrylate” indicate that there may be meta.
  • “(meth) acrylate” is used in the meaning of acrylate or methacrylate.
  • expressions such as “poly (3 to 6)” or “poly (2 to 4)” mean that “poly” is “3 to 6” or “2 to 4” and the like.
  • Examples of mono (meth) acrylates include acryloylmorpholine; hydroxyl group-containing (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; cyclohexane-1,4-dimethanol mono (meta) ) Aliphatic (meth) such as acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Acrylate, phenoxyethyl (meth) acrylate, phenyl (poly) ethoxy (meth) acrylate, 4-cumylphenoxyethyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate Aromatic (meth)
  • Bifunctional (meth) acrylates include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (Meth) acrylate, bisphenol A (poly) ethoxy di (meth) acrylate, bisphenol A (poly) propoxy di (meth) acrylate, bisphenol F (poly) ethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, (poly) ethylene Di (meth) acrylate of ⁇ -caprolactone adduct of glycol di (meth) acrylate hydroxybivalate neopentyl glycol (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), bisphenol And the like epoxy acrylates such as Le A
  • trifunctional or more polyfunctional (meth) acrylates ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, trimethylolpropane (poly) ethoxytri (meth) Poly (meth) acrylates of methylols such as acrylate, trimethylolpropane (poly) propoxytri (meth) acrylate, trimethylolpropane (poly) ethoxy (poly) propoxytri (meth) acrylate; pentaerythritol tri (meth) acrylate, Pentaerythritol (poly) ethoxytetra (meth) acrylate, pentaerythritol (poly) propoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate Poly (meth)
  • Examples of (poly) ester (meth) acrylate include di (meth) acrylate of (poly) ester diol.
  • (Poly) ester diol can be obtained by reaction of a diol compound with a dibasic acid or an anhydride thereof.
  • propylene glycol having a higher degree of polymerization 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8 -Octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-di C1- such as methanol 12 aliphatic glycols or poly (C2-C4 alkylene) glycols; bisphenol A (poly) C2-C3 alkoxy diols such as bisphenol A (poly) ethoxydiol or bisphenol A (poly) propoxydiol; And polyester diol which is a reaction product with
  • Examples of the organic polyisocyanate used for the synthesis of the urethane (meth) acrylate oligomer include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.
  • Linear saturated hydrocarbon isocyanates such as: isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate; 4-tolylene diisocyanate, 1,3-xylylene diisocyanate, 4-pheni And the like can be given; down diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, aromatic polyisocyanates such as 1,5-naphthalene diisocyanate.
  • the (poly) ester (meth) acrylate oligomer As said (poly) ester (meth) acrylate oligomer, the (poly) ester (meth) acrylate oligomer etc. which are obtained by reaction of said (poly) ester diol and (meth) acrylic acid etc. are mentioned, for example.
  • an epoxy (meth) acrylate oligomer the epoxy (meth) acrylate oligomer obtained by reaction with an epoxy resin and (meth) acrylic acid is mentioned.
  • the epoxy resin used here is preferably an epoxy resin having a plurality of epoxy groups such as bisphenol A epoxy resin.
  • the content of the (meth) acrylate (B) is usually 0% by mass to 94% by mass when the solid content of the resin composition of the present invention is 100% by mass. Or less, preferably 0 to 60% by mass, and may be larger than zero when used, but preferably 5 to 60% by mass, preferably 10 to 60% by mass. In some cases, 20 to 80% by mass is also preferable.
  • the content of (meth) acrylate (B) with respect to the total amount of the resin composition of the present invention is usually 0 to 50% by mass, preferably about 0 to 40% by mass, more preferably about 0 to 30% by mass. When used, it may be larger than zero, but is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 5 to 30% by mass.
  • Examples of the photopolymerization initiator (C) used in the resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy -2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one and other acetophenones; 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone and other anthraquinones Thioxanthones such as 2,4-diethyl
  • Irgacure RTM 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopro manufactured by Ciba Specialty Chemicals, Inc. Pan-1-one), Lucylin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) manufactured by BASF, etc. are easily available. Moreover, you may use these individually or in mixture of 2 or more types. Among these, a photopolymerization initiator belonging to acetophenones is preferable, and 1-hydroxycyclohexyl phenyl ketone (Irgacure RTM ) is more preferable.
  • the content of the photopolymerization initiator (C) is 0.1% by mass or more and 10% by mass or less when the solid content of the resin composition of the present invention is 100% by mass, Preferably they are 1 mass% or more and 7 mass% or less. Further, the content of the photopolymerization initiator (C) relative to 100% by mass of the solid content of the resin composition of the present invention may be about 0.2 to 12% by mass. In this case, it is preferably about 0.5 to 10% by mass, more preferably about 1 to 10% by mass, and further preferably about 2 to 8% by mass.
  • the photopolymerization initiator (C) can be used in combination with a curing accelerator (D).
  • the curing accelerator (D) that can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, 4-dimethylaminobenzoic acid isoamyl ester, amines such as EPA, And hydrogen donors such as 2-mercaptobenzothiazole.
  • the amount of these curing accelerators used is 0% by mass or more and 5% by mass or less when the solid content of the resin composition of the present invention is 100% by mass. You may use these individually or in mixture of 2 or more types.
  • a diluent (E) can be used as necessary.
  • a normal temperature (20 ° C.) liquid solvent usually an organic solvent
  • lactones such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -heptalactone, ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -caprolactone; dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Ethers such as diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; carbonates such as ethylene carbonate and prop
  • ester solvents such as ethyl acetate (preferably acetate esters of C2-3 alcohol) and ketones (ketone solvents) are preferable, and C3-C6 aliphatic ketones are more preferable.
  • the content of the diluent (E) is in the range of about 0 to 90% by mass, preferably about 0 to 80% by mass, more preferably the total amount of the resin composition of the present invention. It is about 0 to 60% by mass.
  • the content of the diluent (E) is about 0 to 300% by mass, preferably 0 to 200% by mass, more preferably 0 to About 150% by mass.
  • the content of the component of the composition for example, the content expressed by including “0 to 90% by mass” and 0 as described above does not include the component or is greater than 0 and is 90% by mass. It is meant to be included in the following range.
  • the resin composition of the present invention may be prepared by adding a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, as necessary, in addition to the above-mentioned additives. Etc. can be contained. By including them, each intended functionality can be imparted. Fluorine compounds, silicone compounds, acrylic compounds, etc. as leveling agents, benzotriazole compounds, benzophenone compounds, triazine compounds, etc.
  • UV absorbers hindered amine compounds
  • benzoate compounds as light stabilizers
  • polymerization inhibitors include methoquinone, methylhydroquinone, hydroquinone and the like
  • crosslinking agents include the polyisocyanates and melamine compounds.
  • One of the preferable resin compositions of the present invention contains the urethane (meth) acrylate compound (A) of the present invention and a photopolymerization initiator (C), and further comprises (meth) acrylate (B) or a diluent ( It is a resin composition containing at least any one of E). More specifically, preferred resin compositions of the present invention are as follows. The composition ratio is a ratio relative to the solid content of the resin composition of 100% by mass.
  • the resin composition of the present invention is particularly useful as a resin composition (hard coat agent) for hard coating, and can be used as a molding material for electrical product parts and electronic parts described later.
  • the component (A) and the component (C), and the component (B), the component (D), the component (E) and other components are mixed in any order as necessary. Can be obtained.
  • the hard coat of this invention can be obtained by apply
  • the film thickness after drying the above resin composition using a bar coater or the like may be 0.1 ⁇ m or more and 300 ⁇ m or less, usually 0.1 ⁇ m or more and 50 ⁇ m or less, more preferably 1 ⁇ m. It can be obtained by coating to a thickness of 20 ⁇ m or less, drying as necessary, and irradiating with ultraviolet rays to form a cured film.
  • the film thickness after curing varies depending on the application, and the film thickness after curing is about 0.1 to 300 ⁇ m, preferably about 1 to 250 ⁇ m.
  • the film thickness after curing is usually 0.1 ⁇ m or more and 50 ⁇ m or less, preferably 1 ⁇ m or more and 20 ⁇ m or less, more preferably 10 ⁇ m or less, and further preferably 7 ⁇ m or less.
  • the base film examples include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetyl cellulose, polyether sulfone, and cycloolefin polymer.
  • the film to be used may be one provided with a handle or an easy adhesion layer, one subjected to surface treatment such as corona treatment, or one subjected to release treatment.
  • Examples of the coating method of the resin composition include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, micro reverse gravure coater, and die coater. Examples include coating, dip coating, spin coating, and spray coating.
  • ultraviolet rays are irradiated for curing
  • an electron beam or the like can also be used.
  • an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like is used as a light source, and the light amount, the arrangement of the light source, etc. are adjusted as necessary.
  • a high-pressure mercury lamp it is preferable to cure at a conveyance speed of 5 to 60 m / min for one lamp having an energy of 80 to 120 W / cm 2 .
  • an electron beam accelerator having an energy of 100 to 500 eV, and the photopolymerization initiator (C) may not be used.
  • the cured film of the resin composition of the present invention has adhesiveness to a substrate, hardness, and appropriate flexibility, so that it can be suitably used as a display device material.
  • a display device material For example, spacers used for LCD, EL, rear projection display, color filter materials used for electronic paper, partition material LCD, FED (SED), etc. for separating fine display elements used for PDP, electronic paper, etc. (Thing which plays a role like a pillar for maintaining a gap) or a solid-state imaging device such as a digital camera.
  • the cured product of the photosensitive resin composition of the present invention is a resin particularly suitable for a color filter such as a liquid crystal display device or a solid-state imaging device such as a digital camera, and among these, it is particularly suitable as a color filter.
  • This color filter has a plurality of patterned colored pixels made of a cured product of the photosensitive resin composition of the present invention prepared as described above, or a black matrix and a photo spacer.
  • the display device is a liquid crystal display device, for example, a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter using the photosensitive resin composition of the present invention
  • a polarized light A film or the like is produced in a laminated structure in this order.
  • a color filter layer using the photosensitive resin composition of the present invention is provided on a silicon wafer provided with transfer electrodes and photodiodes, and then a microlens is laminated. It is produced by this.
  • the photosensitive resin composition of the present invention can be used, for example, in printing inks, paints, adhesives, liquid resist inks, and the like.
  • Raw material synthesis example 1 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, 254.3 g (1.0 mol) of dipentaerythritol, 449.7 g (6.2 mol) of acrylic acid, 9 of sulfuric acid .81 g, cupric chloride 1.03 g and toluene 424.7 g were charged, and the reactor was heated and reacted for 12 hours while azeotropically distilling off the produced water with the solvent.
  • the ratio of each component of DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the area ratio (%) of high performance liquid chromatography (HPLC) was 10: 43: 37: 10.
  • the viscosity of the mixture was 6,300 mPa ⁇ s (25 ° C.).
  • Raw material synthesis example 2 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, 254.3 g (1.0 mol) of dipentaerythritol, 432.4 g (6.0 mol) of acrylic acid, 9 of sulfuric acid .81 g, cupric chloride 0.99 g, and toluene 424.7 g were charged, and the reactor was heated and reacted for 12 hours while azeotropically distilling the produced water with the solvent. After the reaction, 849.4 g of toluene was added for dilution, neutralized with 25% aqueous NaOH solution, and then washed 3 times with 600 g of 15% by mass brine.
  • the solvent was distilled off under reduced pressure to obtain 525.3 g of a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 92 mg KOH / g, hydroxyl equivalent: 609.9 g / Eq).
  • the ratio of each component of DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the HPLC area ratio (%) was 12: 45: 36: 7.
  • the viscosity of the mixture was 6,300 mPa ⁇ s (25 ° C.).
  • Raw material synthesis example 3 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, 254.3 g (1.0 mol) of dipentaerythritol, 402.1 g (5.6 mol) of acrylic acid, and sulfuric acid 9 .81 g, cupric chloride 0.92 g, and toluene 424.7 g were charged, and the reactor was heated and reacted for 12 hours while azeotropically distilling off the produced water with the solvent. After the reaction, 849.4 g of toluene was added for dilution, neutralized with 25% aqueous NaOH solution, and then washed 3 times with 600 g of 15% by mass brine.
  • the solvent was distilled off under reduced pressure to obtain 494.9 g of a mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 120 mgKOH / g, hydroxyl equivalent: 467.6 g / Eq).
  • the ratio of each component of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the area ratio (%) of HPLC was 3: 26: 41: 24: 6.
  • the viscosity of the mixture was 6,000 mPa ⁇ s (25 ° C.).
  • Comparative raw material synthesis example 1 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, 254.3 g (1.0 mol) of dipentaerythritol, 497.2 g (6.9 mol) of acrylic acid, 9 of sulfuric acid 9 .81 g, cupric chloride 1.14 g, and toluene 424.7 g were charged, and the reactor was heated and reacted for 12 hours while azeotropically distilling off the produced water with the solvent.
  • Comparative raw material synthesis example 2 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, 254.3 g (1.0 mol) of dipentaerythritol, 380.5 g (5.3 mol) of acrylic acid, 9 of sulfuric acid .81 g, cupric chloride 0.88 g, and toluene 424.7 g were charged, and the reactor was heated and reacted for 12 hours while azeotropically distilling the produced water with the solvent.
  • Example A (Synthesis Example 1) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 1 (hydroxyl value: 80 mgKOH / g, hydroxyl group equivalent: 701) in a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller. .4 g / Eq) 446.47 g (0.64 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform.
  • the content of urethane acrylate is 64% (ratio with respect to the total amount), and the acrylate which is not urethanized (unreacted DPEThexaA and by-product)
  • the content of the acrylate of the pentaerythritol multimer, etc. was 36%.
  • Example B (Synthesis Example 2) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. 9.9 g / Eq) 439.41 g (0.72 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor, and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst, and stirred until uniform.
  • Example C (Synthesis Example 3) A mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 3 (hydroxyl value: 120 mgKOH / g, hydroxyl group equivalent: in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. 467.6 g / Eq) 423.78 g (0.91 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform. The temperature was 50 ° C.
  • Example D (Synthesis Example 4) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller.
  • the solvent (2-butanone) was distilled off under reduced pressure to obtain the urethane acrylate of the present invention.
  • the obtained urethane acrylate had a urethane acrylate content of 74% (ratio to the total amount) and an urethanized acrylate content of 26%.
  • Example E (Synthesis Example 5) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller.
  • Example F (Synthesis Example 6) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller.
  • the NCO content was 0.1% or less. This was the end point of the reaction.
  • Example G (Synthesis Example 7) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller.
  • the NCO content was 0.1% or less. This was the end point of the reaction.
  • the obtained urethane acrylate had a urethane acrylate content of 75% (ratio to the total amount) and an urethanized acrylate content of 25%.
  • Example H (Synthesis Example 8) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. .9 g / Eq) 330.55 g (0.54 mol), 2-butanone 100.00 g, 4-methoxyphenol 0.20 g as a polymerization inhibitor, and dibutyltin dilaurate 0.20 g as a urethanization reaction catalyst were uniformly added. The mixture was stirred until the internal temperature reached 50 ° C.
  • Example I (Synthesis Example 9) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. .9 g / Eq) 337.88 g (0.55 mol), 2-butanone 100.00 g, 4-methoxyphenol 0.20 g as a polymerization inhibitor, dibutyltin dilaurate 0.20 g as a urethanization reaction catalyst, and uniformly added The mixture was stirred until the internal temperature reached 50 ° C.
  • Example J (Synthesis Example 10) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 1 (hydroxyl value: 80 mgKOH / g, hydroxyl group equivalent: 701) in a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller. .4 g / Eq) 331.80 g (0.54 mol), 2-butanone 100.00 g, 4-methoxyphenol 0.20 g as a polymerization inhibitor, dibutyltin dilaurate 0.20 g as a urethanization reaction catalyst, and uniformly added The mixture was stirred until the internal temperature reached 50 ° C.
  • the urethane acrylate thus obtained had a urethane acrylate content of 66% (ratio to the total amount) and a non-urethane acrylate content of 34%.
  • Example K (Synthesis Example 11) A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 3 (hydroxyl value: 120 mgKOH / g, hydroxyl group equivalent: 467) in a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller. .6 g / Eq) 305.74 g (0.50 mol), 2-butanone 100.00 g, 4-methoxyphenol 0.20 g as a polymerization inhibitor, dibutyltin dilaurate 0.20 g as a urethanization reaction catalyst, and uniformly added The mixture was stirred until the internal temperature reached 50 ° C.
  • the urethane acrylate thus obtained had a urethane acrylate content of 74% (ratio to the total amount) and an urethanized acrylate content of 26%.
  • Comparative Synthesis Example 1 A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Comparative Raw Material Synthesis Example 1 (hydroxyl value: 45 mgKOH / g, hydroxyl equivalent) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. : 1246.9 g / Eq) 473.39 g (0.38 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor, 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst, and stirred until uniform. The internal temperature was 50 ° C.
  • the urethane acrylate thus obtained had a urethane acrylate content of 48% (ratio to the total amount) and a non-urethane acrylate content of 52%.
  • Comparative Synthesis Example 2 Mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Comparative Raw Material Synthesis Example 2 (hydroxyl value: 140 mgKOH / g, hydroxyl group) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller (Equivalent: 400.8 g / Eq) 413.28 g (1.03 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform. The internal temperature was 50 ° C.
  • Comparative Synthesis Example 3 A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609.) in a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller. 9 g / Eq) 316.79 g (0.52 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform. The temperature was 50 ° C.
  • TLA-100 hexamethylene diisocyanate trimer
  • Comparative Synthesis Example 4 A mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 3 (hydroxyl value: 120 mgKOH / g, hydroxyl group equivalent: in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. 467.6 g / Eq) 297.93 g (0.49 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor, and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst, and stirred until uniform. The temperature was 50 ° C.
  • Examples 1 to 4 and Comparative Examples 1 to 2 Each component was mix
  • Each of the obtained resin compositions was applied onto a PET film (thickness 125 ⁇ m) subjected to easy adhesion treatment by a bar coater and dried at about 80 to 100 ° C.
  • Each of the obtained coating films was irradiated with ultraviolet rays using an ultraviolet irradiator (JAPAN STORE BATTERY CO, LTD .: CS30L-1-1) to cure the coating films.
  • a PET film (hard coat film) having a hard coat thickness of about 5 ⁇ m was obtained.
  • the curing conditions are as follows.
  • the pencil hardness of the obtained hard coat film was measured using a pencil scratch tester. Specifically, on the polyester film having the cured film to be measured, the pencil is applied with a load of 750 g from the top at a 45 degree angle, and is scratched for about 5 mm. expressed.
  • the film having a cured film obtained by curing the resin composition of the present invention has good hardness, adhesion, and scratch resistance, and does not generate cracks. Compared with the curl is small.
  • Examples 5 to 7 and Comparative Example 3 Each component was mix
  • Curing conditions High pressure mercury lamp: 80 W / cm, lamp height: 10 cm, conveyor speed: 5 m / min (irradiation energy: about 900 mW / cm 2 , about 600 mJ / cm 2 ). Moreover, the unit of numerical values in Table 3 represents “parts by mass”.
  • the cured film obtained by curing the resin composition of the present invention has a high stress at break and elongation at break, and is flexible and tough compared to the comparative examples. Recognize.
  • Examples 8 to 15 Each component was mix
  • “MEK” and “Irg.184” have the same meaning as in Table 1.
  • a PET film (hard coat film) having a hard coat with a film thickness of about 5 ⁇ m was obtained in the same manner as in Examples 1 to 4.
  • the obtained hard coat film was evaluated in the same manner as in Examples 1 to 4, and the results are shown in Table 6 below.
  • the film having a cured film obtained by curing the resin composition of the present invention has good hardness, adhesion, and scratch resistance, and does not generate cracks.
  • the cured film obtained by curing the resin composition of the present invention has good hardness, adhesion, scratch resistance, and maintains the required characteristics as a hard cord such as no occurrence of cracks, while curling is small, It is characterized by having both flexible and tough properties.
  • the hard coat film obtained by curing the resin composition of the present invention has good hardness, adhesion, and scratch resistance, and does not cause curling or cracking. Therefore, the resin composition of the present invention is suitable as a material for plastic films, hard coatings for small cases, color filters, black matrices, and spacers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Abstract

Cette invention concerne un composé de (méth)acrylate d'uréthanne (A) obtenu par réaction (I) de l'un quelconque des mélanges suivants (i) un mélange de poly(méth)acrylates de dipentaérythritol (a) qui comprend au moins deux composés choisis dans un groupe constitué par un tri(méth)acrylate de dipentaérythritol, un tétra(méth)acrylate de dipentaérythritol, un penta(méth)acrylate de dipentaérythritol, et un hexa(méth)acrylate de dipentaérythritol et qui a un indice d'hydroxyle de 80 à 120 mg-KOH/g (ci-après désigné mélange (a)), (ii) à la fois le mélange (a) et du glycérol, et (iii) tout le mélange (a), du glycérol, et un (méth)acrylate de polyol aliphatique C2-5 (di- à tétrol) avec (II) un composé de polyisocyanate (b) comprenant un composé de diisocyanate. Une composition de résine comprenant le composé de (méth)acrylate d'uréthanne (A) et un initiateur de photopolymérisation (C), un objet durci formé à partir de la composition de résine, un matériau de revêtement dur comprenant la composition de résine, et un revêtement dur sont également décrits.
PCT/JP2010/003830 2009-06-17 2010-06-09 Composé de (méth)acrylate d'uréthanne et composition de résine le contenant Ceased WO2010146801A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020117028584A KR101664003B1 (ko) 2009-06-17 2010-06-09 우레탄(메타)아크릴레이트 화합물 및 그것을 함유하는 수지 조성물
JP2011519522A JP5757664B2 (ja) 2009-06-17 2010-06-09 ウレタン（メタ）アクリレート化合物及びそれを含有する樹脂組成物
CN201080026345.4A CN102803332B (zh) 2009-06-17 2010-06-09 氨基甲酸酯(甲基)丙烯酸酯化合物和包含该化合物的树脂组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009143890 2009-06-17
JP2009-143890 2009-06-17

Publications (1)

Publication Number Publication Date
WO2010146801A1 true WO2010146801A1 (fr) 2010-12-23

Family

ID=43356135

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/003830 Ceased WO2010146801A1 (fr) 2009-06-17 2010-06-09 Composé de (méth)acrylate d'uréthanne et composition de résine le contenant

Country Status (5)

Country Link
JP (1) JP5757664B2 (fr)
KR (1) KR101664003B1 (fr)
CN (1) CN102803332B (fr)
TW (1) TWI482791B (fr)
WO (1) WO2010146801A1 (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012121312A1 (fr) * 2011-03-08 2012-09-13 日本合成化学工業株式会社 Composition de résine durcissable sous énergie active et agent de revêtement
CN103314051A (zh) * 2011-01-28 2013-09-18 赢创罗姆有限公司 抗冲改性的反应性树脂
JP2013241503A (ja) * 2012-05-18 2013-12-05 Mitsubishi Rayon Co Ltd 多官能ウレタン（メタ）アクリレート、活性エネルギー線硬化性樹脂組成物及び微細凹凸構造を表面に有する物品
KR20140112433A (ko) 2013-03-13 2014-09-23 아라까와 가가꾸 고교 가부시끼가이샤 광 경화형 수지 조성물 및 이를 이용하여 얻을 수 있는 광학용 필름
JP2016104859A (ja) * 2014-11-25 2016-06-09 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びコーティング剤
WO2016194765A1 (fr) * 2015-06-04 2016-12-08 Dic株式会社 Résine de (méth)acrylate d'uréthane et film stratifié
JP2017002105A (ja) * 2015-06-04 2017-01-05 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
JP2017082204A (ja) * 2015-10-22 2017-05-18 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びコーティング剤
JP2017115028A (ja) * 2015-12-24 2017-06-29 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びこれを含有してなるコーティング剤
JP2017179368A (ja) * 2016-03-29 2017-10-05 荒川化学工業株式会社 活性エネルギー線硬化型組成物及びコーティングフィルム
JP2017203068A (ja) * 2016-05-10 2017-11-16 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びコーティング剤
JP2017226719A (ja) * 2016-06-20 2017-12-28 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
JP2017226720A (ja) * 2016-06-20 2017-12-28 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
JP2017226718A (ja) * 2016-06-20 2017-12-28 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
WO2018181972A1 (fr) * 2017-03-31 2018-10-04 日本合成化学工業株式会社 Composition de résine durcissable par rayonnement d'énergie active et agent de revêtement
WO2018181680A1 (fr) 2017-03-29 2018-10-04 東洋インキＳｃホールディングス株式会社 Composition de couleur pour élément d'imagerie à semi-conducteurs
KR20190019944A (ko) 2016-06-20 2019-02-27 디아이씨 가부시끼가이샤 우레탄(메타)아크릴레이트 수지 및 적층 필름
WO2019124048A1 (fr) * 2017-12-19 2019-06-27 Dic株式会社 Résine (méth)acrylate uréthane, composition de résine durcissable, objet durci, et film stratifié
JP2019108479A (ja) * 2017-12-19 2019-07-04 Dic株式会社 活性エネルギー線硬化性樹脂組成物、硬化物、積層フィルム、加飾フィルム及び物品
KR20240007080A (ko) 2022-07-07 2024-01-16 디아이씨 가부시끼가이샤 우레탄(메타)아크릴레이트 수지, 활성 에너지선 경화성조성물, 경화물 및 적층 필름
JP7711998B1 (ja) 2024-09-09 2025-07-23 大成ファインケミカル株式会社 硬化性樹脂組成物及びその硬化物
JP2026050119A (ja) * 2024-09-09 2026-03-19 大成ファインケミカル株式会社 硬化性樹脂組成物及びその硬化物

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101501686B1 (ko) * 2012-05-31 2015-03-11 주식회사 엘지화학 하드코팅 필름
KR101379491B1 (ko) 2012-05-31 2014-04-01 주식회사 엘지화학 하드코팅 필름 및 이의 제조방법
KR101436617B1 (ko) 2012-05-31 2014-09-02 주식회사 엘지화학 하드코팅 필름
KR101470465B1 (ko) 2012-08-23 2014-12-08 주식회사 엘지화학 하드코팅 필름
JP5839250B1 (ja) * 2014-01-22 2016-01-06 Dic株式会社 硬化性組成物、その硬化物、成形品及びディスプレイ部材
WO2016068201A1 (fr) * 2014-10-31 2016-05-06 凸版印刷株式会社 Matériau de boîtier extérieur pour dispositif de stockage d'énergie
JP2017057349A (ja) * 2015-09-18 2017-03-23 日本化薬株式会社 ポリウレタン化合物及びそれを含有する樹脂組成物
TWI572662B (zh) * 2015-12-30 2017-03-01 奇美實業股份有限公司 熱可塑性樹脂組成物及其所形成的成型品
TW201823343A (zh) * 2016-12-23 2018-07-01 奇美實業股份有限公司 熱可塑性樹脂組成物及其所形成的成型品
TWI737908B (zh) * 2017-04-13 2021-09-01 日商荒川化學工業股份有限公司 胺基甲酸酯（甲基）丙烯酸酯、活性能量射線硬化性樹脂組成物、硬化物及薄膜
TWI736777B (zh) * 2017-06-13 2021-08-21 日商荒川化學工業股份有限公司 胺基甲酸酯（甲基）丙烯酸酯、活性能量射線硬化性樹脂組成物、硬化物及薄膜
CN107880245B (zh) * 2017-11-13 2020-12-08 安庆飞凯新材料有限公司 一种芳香族聚氨酯六丙烯酸酯的制备方法
JP7105502B2 (ja) * 2020-11-12 2022-07-25 根上工業株式会社 ウレタン（メタ）アクリレート含有組成物、光硬化性樹脂組成物、その硬化物、ハードコート剤、及びハードコート層付き基材
JP2022180796A (ja) * 2021-05-25 2022-12-07 Dic株式会社 活性エネルギー線硬化性組成物、硬化物及びフィルム

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5984926A (ja) * 1982-11-05 1984-05-16 Mitsui Petrochem Ind Ltd 被覆用硬化型樹脂組成物
JPS5986666A (ja) * 1982-11-09 1984-05-18 Mitsui Petrochem Ind Ltd 被覆用硬化型樹脂組成物
WO2009147092A1 (fr) * 2008-06-06 2009-12-10 Cytec Surface Specialties, S.A. Compositions de polyuréthane aqueuses durcissables par rayonnement
WO2010090116A1 (fr) * 2009-02-04 2010-08-12 日本化薬株式会社 Composition de résine durcissable par un rayonnement d'énergie actinique pour revêtement dur et son utilisation

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0948934A (ja) 1995-08-08 1997-02-18 Nippon Kayaku Co Ltd 紫外線硬化型樹脂組成物及びハードコート剤
JPH09145903A (ja) 1995-11-27 1997-06-06 Dainippon Printing Co Ltd 反射防止フィルム
JP3515447B2 (ja) 1998-10-14 2004-04-05 株式会社巴川製紙所 反射防止材料及びそれを用いた偏光フィルム
KR100635550B1 (ko) * 1998-12-09 2006-10-18 니폰 가야꾸 가부시끼가이샤 경질 코팅물질 및 이를 포함하는 막
JP2001113648A (ja) 1999-10-19 2001-04-24 Nippon Kayaku Co Ltd 放射線硬化型樹脂組成物の硬化皮膜を有するフィルム
US6972143B2 (en) * 2003-10-27 2005-12-06 Kyle Baldwin Protective U.V. curable cover layer for optical media
JP5516685B2 (ja) * 2012-10-03 2014-06-11 東洋インキＳｃホールディングス株式会社 導電性組成物、およびそれを用いてなる導電膜、ならびに該導電膜を有する積層体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5984926A (ja) * 1982-11-05 1984-05-16 Mitsui Petrochem Ind Ltd 被覆用硬化型樹脂組成物
JPS5986666A (ja) * 1982-11-09 1984-05-18 Mitsui Petrochem Ind Ltd 被覆用硬化型樹脂組成物
WO2009147092A1 (fr) * 2008-06-06 2009-12-10 Cytec Surface Specialties, S.A. Compositions de polyuréthane aqueuses durcissables par rayonnement
WO2010090116A1 (fr) * 2009-02-04 2010-08-12 日本化薬株式会社 Composition de résine durcissable par un rayonnement d'énergie actinique pour revêtement dur et son utilisation

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103314051A (zh) * 2011-01-28 2013-09-18 赢创罗姆有限公司 抗冲改性的反应性树脂
CN103380157B (zh) * 2011-03-08 2015-04-01 日本合成化学工业株式会社 活性能量射线固化性树脂组合物以及涂布剂
JP2012197436A (ja) * 2011-03-08 2012-10-18 Nippon Synthetic Chem Ind Co Ltd:The 活性エネルギー線硬化性樹脂組成物及びコーティング剤
CN103380157A (zh) * 2011-03-08 2013-10-30 日本合成化学工业株式会社 活性能量射线固化性树脂组合物以及涂布剂
WO2012121312A1 (fr) * 2011-03-08 2012-09-13 日本合成化学工業株式会社 Composition de résine durcissable sous énergie active et agent de revêtement
JP2013241503A (ja) * 2012-05-18 2013-12-05 Mitsubishi Rayon Co Ltd 多官能ウレタン（メタ）アクリレート、活性エネルギー線硬化性樹脂組成物及び微細凹凸構造を表面に有する物品
KR20140112433A (ko) 2013-03-13 2014-09-23 아라까와 가가꾸 고교 가부시끼가이샤 광 경화형 수지 조성물 및 이를 이용하여 얻을 수 있는 광학용 필름
JP2016104859A (ja) * 2014-11-25 2016-06-09 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びコーティング剤
WO2016194765A1 (fr) * 2015-06-04 2016-12-08 Dic株式会社 Résine de (méth)acrylate d'uréthane et film stratifié
JP2017002105A (ja) * 2015-06-04 2017-01-05 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
JP2017082204A (ja) * 2015-10-22 2017-05-18 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びコーティング剤
JP2017115028A (ja) * 2015-12-24 2017-06-29 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びこれを含有してなるコーティング剤
JP2017179368A (ja) * 2016-03-29 2017-10-05 荒川化学工業株式会社 活性エネルギー線硬化型組成物及びコーティングフィルム
KR20170113306A (ko) * 2016-03-29 2017-10-12 아라까와 가가꾸 고교 가부시끼가이샤 활성 에너지선 경화형 조성물 및 코팅 필름
KR102285267B1 (ko) 2016-03-29 2021-08-02 아라까와 가가꾸 고교 가부시끼가이샤 활성 에너지선 경화형 조성물 및 코팅 필름
JP2017203068A (ja) * 2016-05-10 2017-11-16 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びコーティング剤
KR20190019944A (ko) 2016-06-20 2019-02-27 디아이씨 가부시끼가이샤 우레탄(메타)아크릴레이트 수지 및 적층 필름
JP2017226718A (ja) * 2016-06-20 2017-12-28 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
JP2017226720A (ja) * 2016-06-20 2017-12-28 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
JP2017226719A (ja) * 2016-06-20 2017-12-28 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
US11614574B2 (en) 2017-03-29 2023-03-28 Toppan Printing Co., Ltd. Coloring composition for solid-state imaging element
WO2018181680A1 (fr) 2017-03-29 2018-10-04 東洋インキＳｃホールディングス株式会社 Composition de couleur pour élément d'imagerie à semi-conducteurs
WO2018181972A1 (fr) * 2017-03-31 2018-10-04 日本合成化学工業株式会社 Composition de résine durcissable par rayonnement d'énergie active et agent de revêtement
WO2019124048A1 (fr) * 2017-12-19 2019-06-27 Dic株式会社 Résine (méth)acrylate uréthane, composition de résine durcissable, objet durci, et film stratifié
JP2019108479A (ja) * 2017-12-19 2019-07-04 Dic株式会社 活性エネルギー線硬化性樹脂組成物、硬化物、積層フィルム、加飾フィルム及び物品
JP7009973B2 (ja) 2017-12-19 2022-01-26 Dic株式会社 活性エネルギー線硬化性樹脂組成物、硬化物、積層フィルム、加飾フィルム及び物品
KR20240007080A (ko) 2022-07-07 2024-01-16 디아이씨 가부시끼가이샤 우레탄(메타)아크릴레이트 수지, 활성 에너지선 경화성조성물, 경화물 및 적층 필름
JP7711998B1 (ja) 2024-09-09 2025-07-23 大成ファインケミカル株式会社 硬化性樹脂組成物及びその硬化物
JP2026050118A (ja) * 2024-09-09 2026-03-19 大成ファインケミカル株式会社 硬化性樹脂組成物及びその硬化物
JP2026050119A (ja) * 2024-09-09 2026-03-19 大成ファインケミカル株式会社 硬化性樹脂組成物及びその硬化物

Also Published As

Publication number Publication date
TWI482791B (zh) 2015-05-01
JP5757664B2 (ja) 2015-07-29
CN102803332B (zh) 2015-05-06
CN102803332A (zh) 2012-11-28
KR101664003B1 (ko) 2016-10-10
JPWO2010146801A1 (ja) 2012-11-29
TW201105694A (en) 2011-02-16
KR20120052192A (ko) 2012-05-23

Similar Documents

Publication Publication Date Title
JP5757664B2 (ja) ウレタン（メタ）アクリレート化合物及びそれを含有する樹脂組成物
JP5679465B2 (ja) 紫外線硬化型ハードコート樹脂組成物
JP5557274B2 (ja) 紫外線硬化型ハードコート樹脂組成物、それを用いたハードコートフィルム及びハードコート成形物
JP5692804B2 (ja) 光学レンズシート用エネルギー線硬化型樹脂組成物及びその硬化物
US20080255264A1 (en) Low Viscosity Multi-Functional Urethane Acrylate Oligomer-Containing High Solid Uv Curable Coating Compostion
JPWO2010090116A1 (ja) 活性エネルギー線硬化型ハードコート用樹脂組成物とその用途
JP5885021B2 (ja) ハードコートフィルム
JP5057367B2 (ja) 活性エネルギー線硬化型樹脂組成物及びその硬化物
WO2016121706A1 (fr) Composition de résine photosensible et produit durci associé
JP2010241917A (ja) 樹脂組成物
JP2009001596A (ja) ポリウレタン化合物、それを含む感光性樹脂組成物及びその硬化物とそれを有するフィルム
JP5812328B2 (ja) 活性エネルギー線硬化型樹脂組成物及びこれを用いたフィルム
JP5083830B2 (ja) 光学レンズシート用エネルギー線硬化型樹脂組成物及び光学レンズシート
JP2011033875A (ja) 光学レンズ用エネルギー線硬化型樹脂組成物及び光学レンズ
WO2012029361A1 (fr) Composition durcissable
JP2017171891A (ja) ポリウレタン（メタ）アクリレート、組成物、硬化物
JP6475571B2 (ja) （メタ）アクリレート化合物及び感光性樹脂組成物
JP2019104907A (ja) 活性エネルギー線硬化性樹脂組成物及びコーティング剤
KR20200090153A (ko) 활성 에너지선 경화성 수지 조성물 및 코팅제
JP2018080273A (ja) 活性エネルギー線硬化性樹脂組成物、及び、その製造方法
JP5429832B2 (ja) ウレタン（メタ）アクリレート化合物
JP2025099025A (ja) 活性エネルギー線硬化性ハードコート剤、ハードコート層および無機酸化物膜付き基材
JP2012171103A (ja) 光学シート用エネルギー線硬化型樹脂組成物及びその硬化物
JP2019104908A (ja) 活性エネルギー線硬化性樹脂組成物及びコーティング剤
JP2017206609A (ja) ポリウレタン（メタ）アクリレート、及びその組成物、硬化物

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080026345.4

Country of ref document: CN

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

Ref document number: 10789185

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2011519522

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20117028584

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: 10789185

Country of ref document: EP

Kind code of ref document: A1