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WO2016031952A1 - Composé polyuréthane et composition de résine le contenant - Google Patents

Composé polyuréthane et composition de résine le contenant Download PDF

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Publication number
WO2016031952A1
WO2016031952A1 PCT/JP2015/074357 JP2015074357W WO2016031952A1 WO 2016031952 A1 WO2016031952 A1 WO 2016031952A1 JP 2015074357 W JP2015074357 W JP 2015074357W WO 2016031952 A1 WO2016031952 A1 WO 2016031952A1
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WO
WIPO (PCT)
Prior art keywords
compound
meth
acrylate
polyol
resin composition
Prior art date
Application number
PCT/JP2015/074357
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English (en)
Japanese (ja)
Inventor
英照 亀谷
貴文 水口
隼 本橋
Original Assignee
日本化薬株式会社
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Filing date
Publication date
Application filed by 日本化薬株式会社 filed Critical 日本化薬株式会社
Priority to KR1020177004949A priority Critical patent/KR20170047240A/ko
Priority to CN201580046776.XA priority patent/CN107075069A/zh
Publication of WO2016031952A1 publication Critical patent/WO2016031952A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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

Definitions

  • This invention relates to the resin composition containing the urethane (meth) acrylate which introduce
  • urethane (meth) acrylate which is a reaction product of a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate compound, has been widely used for applications such as coating agents, adhesives, and photoresists.
  • a urethane (meth) acrylate compound is designed based on a highly transparent polyol compound and an aliphatic or alicyclic polyisocyanate. To do.
  • hydrogenated polybutadiene is selected as a polyol compound to improve yellowing or weather resistance when exposed to more severe conditions.
  • urethane (meth) acrylate is produced using hydrogenated polybutadiene polyol. Although it is excellent in weather resistance as a cured product, it is considered that the hydrogenated polybutadiene skeleton has very high hydrophobicity and is limited in compatibility with monomers and additives that can be blended as a composition. In addition, since it is produced as a urethane (meth) acrylate resin without dilution, the actual industrialization has a high viscosity and may cause problems in terms of workability.
  • urethane (meth) acrylate in LCD (liquid crystal display) applications have become active.
  • patent document 3 it is utilized as a photocurable adhesive composition used for bonding of an optical display or a touch sensor using a polybutadiene-based (meth) acrylate oligomer and a urethane (meth) acrylate oligomer.
  • urethane (meth) acrylate it is presumed that a product having excellent flexibility and higher weather resistance and light resistance will be required in the future.
  • Patent Document 4 describes the application of urethane (meth) acrylate using a polyol compound having no aromatic ring to an LCD optical member.
  • Optical member applications such as these display applications require urethane (meth) acrylates to have higher weather resistance, light resistance, improved cured film properties, and improved compatibility with other resins, monomers, and additives. Further, in the industrialization, detailed design of urethane (meth) acrylate materials and compositions having excellent workability will be required in the future, assuming an actual production line.
  • An object of the present invention is to provide a resin composition that improves the above requirements, provides a cured film having excellent weather resistance and light resistance and excellent flexibility, and has a low shrinkage upon curing.
  • the present invention provides (1) the following compound (A), compound (B), and compound (C): (number of moles of isocyanate group of compound (B))> (number of moles of hydroxyl group of compound (A)) + Polyurethane resin (E) obtained by reacting in the relationship of + number of moles of hydroxyl group of compound (C) and then reacting with compound (D), Compound (A): Polyol compound compound (B): Polyisocyanate compound compound (C): (Meth) acrylate compound compound (D) having at least one hydroxyl group: Polyol compound (2) Polyol compound (A) is hydrogenated The polyurethane resin (E) according to (1), which contains at least one polyol compound selected from polybutadiene polyol, polybutadiene polyol, polyether polyol, and polycarbonate polyol, (3) The polyurethane resin (E) according to (1) or (2), wherein the polyisocyanate compound (B) is an aliphatic diis
  • the polyol compound (D) is charged so that the number of moles of hydroxyl groups in (D) exceeds the number of remaining isocyanate groups, and the isocyanate group and unreacted polyol compound (D) are contained as a plasticizer (1).
  • Functional resin composition (8) The photosensitive resin composition according to (7), wherein the polymerizable compound (G) is an alkyl (meth) acrylate or an alkylene (meth) acrylate, (9) The photosensitive resin composition according to (7) or (8), which contains a photopolymerization initiator (H), (10) A cured product of the photosensitive resin composition according to any one of (7) to (9), About.
  • the cured film of the photosensitive resin composition containing the polyurethane compound of the present invention is excellent in flexibility, weather resistance and light resistance, and in addition to optical applications that need to maintain transparency, ink, plastic paint, paper printing , Metal coating, furniture coating, various coating fields, linings, adhesives, as well as many fields such as insulating varnishes, insulating sheets, laminates, printed circuit boards, resist inks, and semiconductor encapsulants in the electronics field Is possible.
  • the polyurethane resin (E) of the present invention first reacts with the polyol compound (A) and the polyisocyanate compound (B) (hereinafter referred to as the first reaction), and then has at least one hydroxyl group for the remaining isocyanate groups.
  • the (meth) acrylate compound (C) having a reaction hereinafter referred to as a second reaction
  • the polyol compound (D) is reacted with a remaining isocyanate group (hereinafter referred to as a third reaction).
  • polyether polyols such as polybutylene glycol, polytetramethylene glycol, polypropylene glycol and polyethylene glycol, polyethylene glycol adipate, poly 1,4- Polyester polyols such as butanediol adipate and polycaprolactone, glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and neopentylglycol, cyclohexanedimethylol, hydrogenated bisphenol A, hydrogenated bisphenol F, spiro skeleton -Containing alcohols, alicyclic alcohols such as tricyclodecane dimethylol and pentacyclopentadecane dimethylol and their alkylene oxy Iodide adduct, branched or linear long chain alkyl polyol such as polyether polyols such as polybutylene glycol, polytetram
  • hydrogenated polybutadiene polyol, polybutadiene polyol, polyether polyol, and polycarbonate polyol are preferable in maintaining the flexibility and transparency of the photosensitive resin composition of the present invention, and hydrogen is used from the viewpoint of imparting flexibility.
  • Polybutadiene polyol and polybutadiene polyol are particularly preferred, and polycarbonate polyol is particularly preferred from the viewpoint of imparting heat resistance, hardness and adhesive strength.
  • the hydroxyl value is preferably 10 to 300 mg ⁇ KOH / g, more preferably 15 to 250 mg ⁇ KOH / g, and particularly preferably 20 to 150 mg ⁇ KOH / g.
  • polycarbonate polyol is used, the hydroxyl value is preferably 20 to 150 mg ⁇ KOH / g.
  • the polyol compound (A) can be used singly or in combination as long as it is the above compound.
  • the molecular weight of (A) all generally available molecular weight distributions can be used.
  • the number average molecular weight is preferably from 300 to 6000, particularly preferably from 500 to 5000.
  • the polyisocyanate compound (B) used in the first reaction of the present invention is a compound comprising two or more isocyanate groups in one molecule, and examples thereof include aliphatic diisocyanate compounds and aromatic diisocyanates. Compounds, trimers thereof, and the like.
  • the aliphatic diisocyanate compound as used herein means a diisocyanate compound in which an isocyanate group is bonded to a chain carbon atom, and a diisocyanate compound in which an isocyanate group is bonded to a carbon atom of a cyclic saturated hydrocarbon, and an aromatic diisocyanate compound.
  • Examples of the aliphatic diisocyanate compound include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-diisocyanate cyclohexane, 1,4-diisocyanate.
  • aromatic diisocyanate compound examples include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,6-phenylene.
  • diisocyanate monomers such as diisocyanate.
  • an aliphatic diisocyanate compound and a trimer of the aliphatic diisocyanate compound are preferable because the weather resistance of the coating film is improved.
  • the trimer of the aliphatic diisocyanate compound include the above-mentioned aliphatic isocyanate-based isocyanurate-type polyisocyanates, and specific examples include hexamethylene diisocyanate and isophorone diisocyanate. These may be used alone or in a mixture.
  • the first reaction is carried out in an equivalent relationship (B / A> 1: [NCO] / [OH] molar ratio) such that an isocyanate group remains after the reaction.
  • B / A> 1: [NCO] / [OH] molar ratio a large amount of unreacted polyisocyanate compound (B) is present, which may affect the flexibility of the photosensitive resin composition.
  • the preparation ratio is reduced, the molecular weight is increased, which may affect workability deterioration and curability associated with an increase in the viscosity of the photosensitive resin composition.
  • the OH group of the polyol compound (A) is preferably 0.1 to 0.9 mol, preferably 0.4 to 0.00 mol per 1.0 mol of the NCO group of the polyisocyanate compound (B). More preferably, it is 7 mol.
  • the first reaction can be carried out in the absence of a solvent.
  • the following compound in a solvent having no alcoholic hydroxyl group or a polymerizable compound (described later) G) can also be performed.
  • the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dipropylene glycol.
  • Glycol ethers such as dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, esters such as dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as ⁇ -butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. Can be carried out alone or in a mixed organic solvent.
  • the reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C.
  • the end point of the reaction is confirmed by a decrease in the amount of isocyanate.
  • a catalyst may be added for the purpose of shortening the reaction time.
  • this catalyst either a basic catalyst or an acidic catalyst is used.
  • the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphines such as tributylphosphine and triphenylphosphine.
  • acidic catalysts examples include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, titanium tetraisopropoxide, zirconium tetrabutoxide, aluminum chloride, tin octylate, octyltin trilaurate, dibutyltin dilaurate, Mention may be made of Lewis acid catalysts such as octyltin diacetate. The amount of these catalysts added is usually 0.1 to 1 part by weight based on 100 parts by weight of the total weight of the polyol compound (A) and the polyisocyanate compound (B).
  • the (meth) acrylate compound (C) having at least one hydroxyl group used in the second reaction of the present invention is a compound having at least one hydroxyl group and one (meth) acrylate in each molecule.
  • (meth) acrylate compound (C) having at least one hydroxyl group one hydroxyl group is preferred, and 2-hydroxyethyl (meth) acrylate is particularly preferred from the viewpoint of excellent curability and flexibility.
  • a polymerizable compound (G) described later in the present invention may be added during the reaction.
  • the second reaction of the present invention is carried out in an equivalent relationship in which less than an equivalent amount of hydroxyl groups react with the isocyanate group of the intermediate obtained after the first reaction.
  • the OH group of the (meth) acrylate compound (C) having at least one hydroxyl group is 0.01 to 0.00 with respect to 1.0 mol of the NCO group of the intermediate obtained after the first reaction. It is 99 mol, more preferably 0.1 to 0.9 mol, and particularly preferably 0.4 to 0.6 mol.
  • the second reaction of the present invention can also be carried out in the absence of a solvent, but the product has a high viscosity and the above-described solvent and / or polymerizable compound (G) described later in the present invention for improving workability. It is preferable to carry out under mixing.
  • the reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C.
  • the end point of the reaction is confirmed by a decrease in the amount of isocyanate.
  • the aforementioned catalyst may be added for the purpose of shortening the reaction time.
  • a polymerization inhibitor such as 4-methoxyphenol has already been added to the (meth) acrylate compound used as a raw material, but a polymerization inhibitor may be added again during the reaction.
  • examples of such polymerization inhibitors include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-cresol, 3-hydroxythiophenol, Examples include p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, and phenothiazine. The amount used is 0.01 to 1% by weight based on the reaction raw material mixture.
  • the polyurethane resin (E) of the present invention can be obtained by reacting the intermediate obtained in the second reaction with the polyol compound (D) (third reaction).
  • the polyol compound (D) one or more kinds of the same or different kinds as the above-described polyol compound (A) can be selected and used.
  • the same thing as a polyol compound (A) can be used, The example is as above-mentioned.
  • the polyol compound (A) and the polyol compound (D) are the same type of compound (for example, polybutadiene polyol and polybutadiene polyol, polyether polyol and polyether polyol, polycarbonate polyol and polycarbonate polyol, etc.) or the same compound. Is preferred.
  • the third reaction of the present invention is charged in an equivalent relationship such that the isocyanate group of the intermediate obtained after the second reaction is eliminated.
  • the OH group of the polyol compound (D) is preferably 1.0 to 10.0 mol, more preferably 1.0 to 1.0 mol with respect to 1.0 mol of the NCO group of the intermediate obtained after the second reaction.
  • the amount is 9.0 mol, particularly preferably 3.0 to 5.0 mol.
  • the polyol compound (A) reacts with a part of the isocyanate groups of the polyisocyanate compound (B), and the remaining isocyanate groups have a hydroxyl group (meth). Since the polyurethane compound (U1) obtained by the reaction of the acrylate compound (C) and the polyol compound (A) reacts with the polyisocyanate in the first reaction, the isocyanate group of the polyisocyanate compound (B) is converted into the polyol compound (A).
  • the terminal polyisocyanate compound (B) reacts with the (meth) acrylate compound (C) having a hydroxyl group to add a (meth) acryloyl group, and a polyol compound ( And a polyurethane compound (U2) obtained by reacting D).
  • the polyisocyanate compound (B) is preferably bifunctional.
  • the resulting polyurethane compound having a (meth) acryloyl group contains a large amount of monofunctionality.
  • the obtained polyurethane compounds (U1) and (U2) are preferably 0.1 to 99% by weight and more preferably 30 to 95% by weight in the polyurethane resin (E).
  • the monofunctional polyurethane compound as described above has sufficient flexibility and excellent cured properties, it is preferable that such a compound is contained in an amount of 0.1 to 99% by weight. 30 to 95% by weight is more preferable.
  • the weight average molecular weights of the obtained polyurethane compounds (U1) and (U2) are preferably 2000 to 10,000, and more preferably 3000 to 7000.
  • the compound obtained by the first to third reactions of the present invention has a (meth) acryloyl group obtained by reacting the polyol compound (A or D) with all isocyanate groups of the polyisocyanate compound (B).
  • the polyol compound (P1) having no (meth) acryloyl group or the high molecular weight polyol compound (P2) having no (meth) acryloyl group preferably has a weight average molecular weight of 300 to 100,000, preferably 800 to 10, 000 is more preferable.
  • the polyol compound (P1) having no (meth) acryloyl group or the high molecular weight polyol compound (P2) having no (meth) acryloyl group is 0.1 to 99 in the obtained polyurethane resin (E). % By weight is preferable, and 1 to 20% by weight is more preferable.
  • Such a polyol compound (P1) having no (meth) acryloyl group or a high molecular weight polyol compound (P2) having no (meth) acryloyl group can impart high flexibility.
  • a (meth) acrylate compound (C) having a hydroxyl group on all of the isocyanate groups of the polyisocyanate compound (B) is obtained.
  • a compound (T1) having a plurality of (meth) acryloyl groups, an isocyanate group of the polyisocyanate compound (B) are linked by a polyol compound (A), and all of the terminal polyisocyanate compound (B) have a hydroxyl group (meth) acrylate
  • the content of the thus obtained high molecular weight compound (T1) having a plurality of (meth) acryloyl groups and compound (T2) having a plurality of (meth) acryloyl groups is 0.1 to
  • the content is preferably 99% by weight, particularly preferably 1 to 20% by weight.
  • the third reaction of the present invention can also be carried out in the absence of a solvent.
  • the product has a high viscosity and the above-described solvent and / or polymerizable compound (G) described later in the present invention for improving workability. It can also be performed under a mixture of
  • the reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C.
  • the end point of the reaction is confirmed by a decrease in the amount of isocyanate.
  • the aforementioned catalyst may be added for the purpose of shortening the reaction time.
  • the photosensitive resin composition of the present invention may contain the polyurethane resin (E) or the resin composition (F) of the present invention and a polymerizable compound (G) other than the components (E) or (F) as optional components. it can.
  • a polymerizable compound (G) that can be used include a compound having a (meth) acryloyloxy group, a maleimide compound, a (meth) acrylamide compound, and an unsaturated polyester.
  • Specific examples of the compound having a (meth) acryloyloxy group that can be used in combination with the photosensitive resin composition of the present invention include (poly) ester (meth) acrylate (G-1); urethane (meth) acrylate (G-2). ); Epoxy (meth) acrylate (G-3); (poly) ether (meth) acrylate (G-4); alkyl (meth) acrylate or alkylene (meth) acrylate (G-5); having an aromatic ring (meth) ) Acrylate (G-6); (meth) acrylate (G-7) having an alicyclic structure, and the like, but are not limited thereto.
  • a reaction material it can obtain on well-known reaction conditions.
  • the (poly) ester (meth) acrylate (G-1) that can be used in combination with the photosensitive resin composition of the present invention is a general term for (meth) acrylate having one or more ester bonds in the main chain.
  • Acrylate (G-2) is a general term for (meth) acrylate having one or more urethane bonds in the main chain.
  • Epoxy (meth) acrylate (G-3) is a monofunctional or higher functional epoxy compound and (meth).
  • (meth) acrylate obtained by reacting acrylic acid is a generic term for (meth) acrylate having one or more ether bonds in the main chain
  • Alkyl (meth) acrylate or alkylene (meth) acrylate (G-5) is a main chain having a straight chain alkyl, a branched alkyl, a straight chain or a halogen at the terminal.
  • (meth) acrylate (G-6) having an aromatic ring is (meth) acrylate having an aromatic ring in the main chain or side chain.
  • (meth) acrylate (G-7) having an alicyclic structure has an alicyclic structure that may contain an oxygen atom or a nitrogen atom in the structural unit in the main chain or side chain (meth). These are used as a general term for acrylates.
  • Examples of the (poly) ester (meth) acrylate (G-1) that can be used in combination with the photosensitive resin composition of the present invention include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalate.
  • Monofunctional (poly) ester (meth) acrylates such as acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate; hydroxypivalate ester neopentyl glycol di (meth) Acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; trimethylolpropane or glycerin 1 1 mole or more ⁇ - caprolactone Le, .gamma.-butyrolactone, a triol obtained by adding a cyclic lactone compound such as ⁇ - valerolactone mono-, di- or tri (meth) acrylate;
  • a cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone
  • ⁇ -valerolactone Mono- or poly (meth) acrylate of hexaol obtained by adding 1 mol or more of cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone to 1 mol of dipentaerythritol;
  • Diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, hexanediol, and maleic acid, fumaric acid, succinic acid Acids, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, polybasic acids such as 5-sodiumsulfoisophthalic acid, and their reactants (Meth) acrylates of polyester polyols such as: (meth) acrylates of cyclic lactone-modified polyester diols composed of the diol components and polybasic acids and their anhydrides and ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, etc. Multifunctional (pol
  • the urethane (meth) acrylate (G-2) that can be used in combination with the photosensitive resin composition of the present invention includes at least one hydroxy compound (G-2-I) having an (meth) acryloyloxy group and an isocyanate compound (G- A general term for (meth) acrylates obtained by reaction with 2-ro).
  • hydroxy compound (G-2-i) having at least one (meth) acryloyloxy group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy Ring-opening reaction of (meth) acrylate compounds having various hydroxyl groups such as -3-phenoxypropyl (meth) acrylate, and the above-mentioned (meth) acrylate compounds having a hydroxyl group and ⁇ -caprolactone And the like.
  • isocyanate compound (G-2-ro) examples include, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate.
  • Aromatic diisocyanates such as diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; aliphatics such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate Or diisocyanates having an alicyclic structure; one or more burettes of isocyanate monomers or the above diisocyanates Things a trimer polyisocyanates of the isocyanate and the like; the and the isocyanate compound include polyisocyanates obtained by urethane reaction of the polyol compound.
  • a polyol is optionally reacted. It doesn't matter.
  • examples of polyols that can be used include those having 1 to 10 carbon atoms such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.
  • Triols such as alkylene glycol, trimethylolpropane, pentaerythritol, alcohols having a cyclic skeleton such as tricyclodecane dimethylol, bis- [hydroxymethyl] -cyclohexane, and the like; and these polyhydric alcohols and polybasic acids (for example, succinic acid) , Phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.) polyester polyol obtained by reaction with polyhydric alcohol and ⁇ -caprolactone Lactone alcohol, polycarbonate polyol (for example, polycarbonate diol obtained by reaction of 1,6-hexanediol and diphenyl carbonate) or polyether polyol (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A, etc.) Etc
  • the epoxy (meth) acrylate (G-3) that can be used in combination with the photosensitive resin composition of the present invention is a (meth) acrylate obtained by reacting an epoxy resin containing one or more epoxy groups with (meth) acrylic acid. Is a general term.
  • epoxy resins used as raw materials for epoxy (meth) acrylates include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether; bisphenol-A type epoxy resin, bisphenol-F type epoxy Bisphenol-type epoxy compounds such as resins, bisphenol-S type epoxy resins, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compounds; A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane Epoxy Hydrogenated bisphenol-type epoxy compounds such as compounds; Halogenated bisphenol-type epoxy compounds such as brominated bisphenol-A type epoxy resins and brominated bisphenol-F type epoxy resins; Alicyclic diglycidyl such as cyclohex
  • Examples of the (poly) ether (meth) acrylate (G-4) that can be used in combination with the photosensitive resin composition of the present invention include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin-modified butyl ( (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, etc.
  • Alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; ethylene oxide and propylene oxide Copolymer, copolymer of propylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, polyhydric hydroxyl compound such as hydrogenated polybutadiene glycol and the like, and (meth) acrylic acid Induced polyfunctional (meth) acrylates; 1 mol or more of ethylene oxide, propylene oxide, butylene oxide per 1 mol of neopentyl glycol Di diol obtained by adding a cyclic ether (meth) acrylate;
  • Mono-, di-, tri-, or tetra (meth) acrylates of triols obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide to 1 mol of pentaerythritol or ditrimethylolpropane; 1 mol of dipentaerythritol
  • a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide
  • pentaerythritol or ditrimethylolpropane 1 mol of dipentaerythritol
  • examples thereof include polyfunctional (poly) ether (meth) acrylates such as hexaol tri- to hexafunctional (meth) acrylates to which cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide and the like are added in a molar amount or more.
  • alkyl (meth) acrylate or alkylene (meth) acrylate (G-5) examples include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate.
  • Mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter, “poly” is used as a general term for polyfunctionality such as di, tri, tetra, etc.), mono (meth) of glycerin Triols such as acrylate or poly (meth) acrylate, mono- or poly (meth) acrylate of pentaerythritol, mono- or poly (meth) acrylate of ditrimethylolpropane, mono- or poly (meth) acrylate of dipentaerythritol, tetraol, hexa Mono- or poly (meth) acrylates of polyhydric alcohols such as oar;
  • hydroxyl group-containing (meth) acrylic compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • Examples of the (meth) acrylate (G-6) having an aromatic ring that can be used in combination with the photosensitive resin composition of the present invention include monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate. And di (meth) acrylates such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate, but are not limited thereto.
  • Examples of the (meth) acrylate (G-7) having an alicyclic structure that can be used in combination with the photosensitive resin composition of the present invention include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, Monofunctional (meth) acrylates having an alicyclic structure such as cyclopentenyl (meth) acrylate; di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F; tricyclodecane dimethylol di ( Examples include polyfunctional (meth) acrylates having a cyclic structure such as (meth) acrylate; alicyclic (meth) acrylates having an oxygen atom or the like in the structure such as tetrafurfuryl (meth) acrylate, It is not limited to these.
  • Examples of the compound having a (meth) acryloyl group that can be used in combination with the photosensitive resin composition of the present invention include, for example, a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) acrylate, in addition to the above-described compounds.
  • a poly (meth) acrylic polymer (meth) acrylate such as a reaction product of a glycidyl (meth) acrylate polymer and (meth) acrylic acid; a (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; Isocyanuric (meth) acrylates such as (meth) acryloxyethyl isocyanurate; (meth) acrylates having a polysiloxane skeleton; polybutadiene (meth) acrylates, melamine (meth) acrylates, and the like can also be used.
  • maleimide group-containing compound (G-8) examples include Nn-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2- Monofunctional aliphatic maleimides such as maleimidoethyl-propyl carbonate and N-ethyl- (2-maleimidoethyl) carbamate; Alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; N, N-hexamethylene bismaleimide, polypropylene Aliphatic bismaleimides such as glycol-bis (3-maleimidopropyl) ether and bis (2-maleimidoethyl) carbonate; cycloaliphatic such as 1,4-dimaleimidocyclohexane and isophorone bisurethane bis (N-ethylmaleimide) Bismaleimide; with maleimidoacetic acid Ester
  • Examples of the (meth) acrylamide compound (G-9) that can be used in combination with the photosensitive resin composition of the present invention include monofunctional (meth) acrylamides such as acryloylmorpholine and N-isopropyl (meth) acrylamide; Examples thereof include polyfunctional (meth) acrylamides such as (meth) acrylamide.
  • Examples of the unsaturated polyester (G-10) that can be used in combination with the photosensitive resin composition of the present invention include fumaric acid esters such as dimethyl malate and diethyl malate; polyunsaturated such as maleic acid and fumaric acid.
  • the esterification reaction product of carboxylic acid and a polyhydric alcohol can be mentioned.
  • the polymerizable compound (G) that can be used in combination with the photosensitive resin composition of the present invention is a combination of alkyl (meth) acrylate or alkylene (meth) acrylate (G-5) that has low viscosity, excellent light resistance, and excellent workability.
  • the compound is not limited to the above-described compounds, and one or a plurality of compounds can be used in combination without particular limitation as long as the compound has a copolymerizability with the component (E).
  • compounds having a (meth) acryloyloxy group having a long chain of C5 to C35, more preferably C15 to C35, such as alkyl (meth) acrylate or alkylene (meth) acrylate are suitable. This is because a photosensitive resin composition having excellent compatibility and transparency can be obtained by having such a structure.
  • the ratio of the components (E) and (G) is not particularly limited, but the component (G) is 10 to 2000 wt% with respect to 100 wt% of the component (E). %, Preferably 20 to 1000% by weight.
  • photopolymerization initiator (H) used in the photosensitive 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 Acetophenones such as-(methylthio) phenyl] -2-morpholinopropan-1-one; anthrax such as 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Thioxanthones such as 2,4-diethylthio
  • tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester
  • an accelerator such as a benzoic acid derivative.
  • an amount of 100% by weight or less is added to the photopolymerization initiator (H) as necessary.
  • the photosensitive resin composition of the present invention is a non-reactive compound, an inorganic filler, an organic filler, a silane coupling agent, a tackifier, an antifoaming agent, a leveling agent, a plasticizer, an oxidation, depending on the application.
  • Inhibitors, ultraviolet absorbers, flame retardants, pigments, dyes, and the like can be used as appropriate.
  • non-reactive compound examples include a liquid or solid oligomer or resin having low reactivity or non-reactivity, and includes an alkyl (meth) acrylate copolymer, an epoxy resin, liquid polybutadiene, Cyclopentagen derivatives, saturated polyester oligomers, xylene resins, polyurethane polymers, ketone resins, diallyl phthalate polymers (dup resins), petroleum resins, rosin resins, fluorine-based oligomers, silicon-based oligomers, phthalate esters, phosphate esters, Glycol esters, citric acid esters, aliphatic dibasic acid esters, fatty acid esters, epoxy plasticizers, castor oils, terpene hydrogenated resin polyisoprene skeletons, oligomers or polymers having polybutadiene skeletons or xylene skeletons, and That d Ether product, homopolymer, epoxy-modified polybutadiene, and That
  • the inorganic filler examples include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, and glass. , Mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon, and the like. These inorganic fillers may be added with a silane coupling agent, titanate coupling agent, aluminum coupling agent, zirconate coupling agent, or the like, and reacted to form a halogen group, an epoxy group, a hydroxyl group, or a thiol. It can also have a functional group.
  • organic filler examples include benzoguanamine resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, acrylic copolymer, polymethyl methacrylate resin, fluororesin, Nylon 12, nylon 6/66, phenol resin, epoxy resin, urethane resin, polyimide resin and the like can be mentioned.
  • silane coupling agent examples include silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane or ⁇ -chloropropyltrimethoxysilane, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl), and the like.
  • titaniumate coupling agents such as phosphite titanate and bis (dioctylpyrophosphate) ethylene titanate
  • Aluminum coupling agents such as acetoalkoxyaluminum diisopropylate
  • Zirconium coupling agents such as acetylacetone / zirconium complex, etc. be able to.
  • any tackifier, antifoaming agent, leveling agent, plasticizer, antioxidant, ultraviolet absorber, flame retardant, pigment, and dye that can be used in the photosensitive resin composition of the present invention can be used.
  • a thing can be especially used without a restriction
  • the above-described components may be mixed, and the order and method of mixing are not particularly limited.
  • the weight ratio of the various additives in the photocurable transparent adhesive composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, and more preferably. Is 0.02 to 0.5% by weight.
  • the photosensitive resin composition of the present invention does not substantially require a solvent.
  • a solvent for example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetates such as ethyl acetate and butyl acetate, benzene, toluene, xylene and the like It is also possible to dilute and use the photosensitive resin composition of the present invention with other generally used organic solvents such as aromatic hydrocarbons.
  • the photosensitive resin composition of the present invention can be polymerized by irradiation with ultraviolet rays or visible rays having a wavelength of 180 to 500 nm. Further, it can be cured by irradiation with energy rays other than ultraviolet rays or by heat.
  • Examples of the light generation source of ultraviolet light or visible light having a wavelength of 180 to 500 nm include, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, and a short.
  • Examples include arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, and sunlight.
  • the photosensitive resin composition of the present invention is excellent in flexibility, weather resistance and light resistance, and besides optical applications that need to maintain transparency, ink, plastic paint, paper printing, metal coating, furniture coating, etc. It is useful in various fields such as various coating fields, linings, adhesives, as well as insulating varnishes, insulating sheets, laminates, printed boards, resist inks, and semiconductor encapsulants in the electronics field.
  • More specific applications include planographic relief inks, flexographic inks, gravure inks, screen inks and other ink fields, glossy fields, paper coating materials fields, wood coating materials fields, beverage can coating materials or printing ink fields, Soft packaging film coating agent, printing ink or adhesive, thermal paper, thermal film coating agent, printing ink, adhesive, adhesive or optical fiber coating agent, liquid crystal display device, organic EL display device, touch panel type image display device It is useful for applications such as air gap fillers for display devices (fillers for gaps between display devices and face plates).
  • Synthesis example 1 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 (hydrogenated polybutadiene polyol, hydroxyl value: 46.8 mg ⁇ KOH / g) manufactured by Nippon Soda Co., Ltd. was used as a polyol compound. .88 g (0.99 mol), 31.26 g (0.01 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g) manufactured by Asahi Glass Co., Ltd. were charged and the internal temperature was 50 ° C. while stirring. did.
  • Synthesis example 2 2088.31 g of Nippon Soda Co., Ltd. G-2000 (polybutadiene polyol, hydroxyl value: 53.2 mg ⁇ KOH / g) as a polyol compound was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device. (0.99 mol), 31.26 g (0.01 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g) manufactured by Asahi Glass Co., Ltd. was charged, and the internal temperature was adjusted to 50 ° C. while stirring.
  • Synthesis example 3 1998 17 g of T-5652 (polycarbonate polyol, hydroxyl value: 55.6 mg ⁇ KOH / g) manufactured by Asahi Kasei Chemicals Corporation as a polyol compound was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device. (0.99 mol), 9.75 g (0.01 mol) of T-6001 (polycarbonate polyol, hydroxyl value: 115.1 mg ⁇ KOH / g) manufactured by Asahi Kasei Chemicals Co., Ltd., and the internal temperature was 50 ° C. while stirring. did.
  • T-5552 polycarbonate polyol, hydroxyl value: 55.6 mg ⁇ KOH / g
  • tin octylate was used as the urethanization reaction catalyst.
  • 72 g was added and reacted at 80 ° C., and when the NCO content was 0.1% or less, the reaction was terminated, and a resin composition (F-3) containing a polyurethane resin (E-3) was obtained. .
  • Synthesis example 4 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 (hydrogenated polybutadiene polyol, hydroxyl value: 46.8 mg ⁇ KOH / g) manufactured by Nippon Soda Co., Ltd. was used as a polyol compound. .88 g (0.99 mol), 31.26 g (0.01 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g) manufactured by Asahi Glass Co., Ltd. as a polymerizable compound, Shin-Nakamura Chemical Co., Ltd.
  • Formulation Example 1 20 parts by mass of the resin composition (F-1) of Synthesis Example 1, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation Yasuhara Chemical Co., Ltd. Clearon M-105 (aromatic modified hydrogenated terpene resin) 18 parts by mass, JX Nippon Oil & Energy Corporation LV-100 (polybutene) 10 parts by mass, Nippon Soda Co., Ltd. GI- 2000 (1,2-hydrogenated polybutadiene glycol) 20 parts by mass, Osaka Organic Chemical Co., Ltd.
  • S-1800A isostearyl acrylate
  • Bremer LA laauryl acrylate
  • Clearon M-105 aromatic modified hydrogenated terpene resin
  • JX Nippon Oil & Energy Corporation LV-100 polybutene
  • GI- 2000 (1,2-hydrogenated polybut
  • Formulation Example 2 20 parts by mass of the resin composition (F-2) of Synthesis Example 2, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI- manufactured by Nippon Soda Co., Ltd. 2000 (1,2-hydrogenated polybutadiene glycol) 20 parts by mass, Osaka Organic Chemical Co., Ltd.
  • Formulation Example 3 20 parts by mass of the resin composition (F-3) of Synthesis Example 3, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, T- manufactured by Asahi Kasei Chemicals Corporation 5652 (polycarbonate polyol) 20 parts by mass, Osaka Organic Chemical Co., Ltd.
  • S-1800A isostearyl acrylate
  • Bremer LA laauryl acrylate
  • Clearon M-105 aromatically modified hydrogenated terpene resin
  • LV-100 polybutene
  • Formulation Example 4 20 parts by mass of the resin composition (F-4) of Synthesis Example 4, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI- manufactured by Nippon Soda Co., Ltd. 2000 (1,2-hydrogenated polybutadiene glycol) 20 parts by mass, Osaka Organic Chemical Co., Ltd.
  • Formulation Examples 1 to 4 are shown in Table 1, and the following evaluation was performed.
  • Viscosity The viscosity was measured at 25 ° C. using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.).
  • the refractive index (25 ° C.) of the resin was measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).
  • the photosensitive resin composition containing the polyurethane compound of the present invention is excellent in flexibility, weather resistance, light resistance, and transparency, and thus is useful as an optical use member. Furthermore, the cured product of the photosensitive resin composition of the present invention is useful as an adhesive for bonding a transparent display substrate.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
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Abstract

La présente invention concerne une résine de polyuréthane (E) qui a une excellente flexibilité, une résistance aux intempéries et une résistance à la lumière, qui peut conserver une transparence, et est appropriée pour être utilisée dans des applications optiques. La résine de polyuréthane (E) est obtenue par la réaction d'un composé (A), d'un composé (B) et d'un composé (C), en fonction de la relation (nombre de moles de groupes isocyanate de (B)) > (nombre total de moles de groupes hydroxyle de (A) et (C)), puis par la réaction d'un composé (D). Composé (A) : un composé polyol; composé (B) : un composé polyisocyanate; composé (C) : un composé (méth) acrylate qui a au moins un groupe hydroxyle; et un composé (D) : un composé polyol.
PCT/JP2015/074357 2014-08-29 2015-08-28 Composé polyuréthane et composition de résine le contenant WO2016031952A1 (fr)

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CN114685745A (zh) * 2020-12-25 2022-07-01 昭和电工株式会社 氨基甲酸酯(甲基)丙烯酸酯及氨基甲酸酯(甲基)丙烯酸酯树脂的制造方法
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JP6899225B2 (ja) * 2017-01-30 2021-07-07 ダイセル・オルネクス株式会社 活性エネルギー線硬化性組成物
KR101923300B1 (ko) * 2017-02-24 2018-11-29 (주)켐베이스 폴리카보네이트 디올을 함유하는 플렉소 인쇄판용 감광성 수지 조성물
KR102173182B1 (ko) * 2018-11-06 2020-11-02 (주)이녹스첨단소재 Fpic 필름 및 이의 제조방법
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