WO2015083795A1 - Composé de polyuréthane, composition de résine photosensible, procédé pour produire une composition de résine photosensible et produit durci - Google Patents

Composé de polyuréthane, composition de résine photosensible, procédé pour produire une composition de résine photosensible et produit durci Download PDF

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WO2015083795A1
WO2015083795A1 PCT/JP2014/082128 JP2014082128W WO2015083795A1 WO 2015083795 A1 WO2015083795 A1 WO 2015083795A1 JP 2014082128 W JP2014082128 W JP 2014082128W WO 2015083795 A1 WO2015083795 A1 WO 2015083795A1
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compound
meth
acrylate
resin composition
photosensitive resin
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PCT/JP2014/082128
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English (en)
Japanese (ja)
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英照 亀谷
貴文 水口
隼 本橋
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日本化薬株式会社
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Priority to CN201480065049.3A priority Critical patent/CN105849146A/zh
Publication of WO2015083795A1 publication Critical patent/WO2015083795A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • 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
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy 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
    • C08G18/6204—Polymers of olefins
    • C08G18/6208—Hydrogenated polymers of conjugated dienes
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate

Definitions

  • the present invention relates to a polyurethane compound containing urethane (meth) acrylate having a hydrogenated polybutadiene polyol as a main skeleton, a photosensitive resin composition, a method for producing the photosensitive resin composition, and a cured product. Furthermore, since the cured film of the resin composition of the present invention is excellent in flexibility, transparency, moisture resistance, adhesion to a substrate, and has little curing shrinkage, it is particularly useful for bonding applications such as optical films for display devices. is there.
  • 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.
  • the hydrogenated polybutadiene skeleton has very high hydrophobicity and is limited in compatibility with monomers and additives that can be blended as a composition.
  • the hydrogenated polybutadiene polyol used has a relatively high iodine value, suggesting the possibility that it does not give properties that satisfy the currently required weather resistance and light resistance.
  • the actual industrialization since it is manufactured 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.
  • 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 estimated that the thing excellent in a softness
  • Patent Document 4 describes the application of urethane (meth) acrylate using a polyol compound having no aromatic ring to an LCD optical member.
  • urethane (meth) acrylates require 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.
  • the present invention improves the above-mentioned requirements, gives a cured film having excellent weather resistance and light resistance, and excellent flexibility, and can be a resin composition having a low shrinkage during curing, It aims at providing the photosensitive resin composition containing this, the manufacturing method of this photosensitive resin composition, and the hardened
  • a photosensitive resin composition comprising the polyurethane compound (E) according to any one of (1) to (5) and a polymerizable compound (F) other than (E), (7) The photosensitive resin composition according to (6), wherein the polymerizable compound (F) is an alkyl (meth) acrylate or an alkylene (meth) acrylate, (8) The method for producing a photosensitive resin composition according to (6) or (7), wherein the polyurethane compound (E) is synthesized in a polymerizable compound (F) mixed system, (9) The photosensitive resin composition according to (6) or (7), which contains a photopolymerization initiator (G), (10) A cured product of the photosensitive resin composition according to any one of (6) to (8), About.
  • the cured film of the photosensitive resin composition containing the polyurethane compound of the present invention has excellent flexibility, weather resistance, light resistance, and optical use that needs to maintain transparency, as well as ink, plastic paint, In various fields such as paper printing, metal coating, furniture coating, lining, adhesives, as well as insulating varnishes, insulating sheets, laminates, printed circuit boards, resist inks, semiconductor encapsulants in the electronics field Application is possible.
  • the polyurethane compound (E) of the present invention is first reacted (hereinafter referred to as the first reaction) with the diol compound (D) other than the hydrogenated polybutadiene polyol (A) and the compound (A) and the polyisocyanate compound (B).
  • the (meth) acrylate compound (C) having at least one hydroxyl group is reacted with the remaining isocyanate group (hereinafter referred to as a second reaction).
  • any hydrogenated reduction product of a general polybutadiene polyol can be used.
  • the iodine value is more preferably 20 or less, and particularly preferably 15 or less.
  • the molecular weight of (A) all generally available molecular weight distributions can be used, but those having a number average molecular weight of 500 to 5,000 are particularly preferred when a balance between flexibility and curability is achieved. Those of 500 to 3000 are particularly preferred.
  • diol compound (D) other than the compound (A) used in the first reaction of the present invention include, for example, polyethers such as polyethylene glycol, polybutylene glycol, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol.
  • Polyols polyethylene glycol adipate, poly 1,4-butanediol adipate, polyester polyols such as polycaprolactone, glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and neopentyl glycol, cyclohexane dimethylol, Hydrogenated bisphenol A, hydrogenated bisphenol F, spiro skeleton-containing alcohol, tricyclodecane dimethylol and pentacyclopentadecane dimethylo Alicyclic alcohols such as these and alkylene oxide adducts thereof, branched or linear long-chain alkyl diols such as hydrogenated polybutadiene diols, bisphenols such as bisphenol A and bisphenol F, and alkylene oxide adducts of bisphenols, Examples include polyols such as methylolpropane, ditrimethylolprop
  • polyether polyols in order to improve flexibility and compatibility in the cured product of the photosensitive resin composition of the present invention.
  • the molecular weight of the diol compound (D) other than the compound (A) all generally available molecular weight distributions can be used, but in particular, when the balance between flexibility and curability is balanced, the number average molecular weight Is preferably from 500 to 6000, particularly preferably from 500 to 4000.
  • the diol compound (D) other than the compound (A) that is particularly preferably used is a polyether polyol having a molecular weight of 500 to 4000.
  • diol compound (D) other than hydrogenated polybutadiene polyol (A) and (A) when diol compound (D) other than hydrogenated polybutadiene polyol (A) and (A) is used for reaction, diol compound (D) other than hydrogenated polybutadiene (A) and (A) is used.
  • the use ratio is not particularly limited, but the component (A) :( D) is preferably in a molar ratio of 9.999: 0.001 to 2: 8, more preferably 9.999: 0.001 to 5: 5, Particularly preferred is 9.999: 0.001 to 7: 3.
  • 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 compounds include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,6-phenylene. And 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 charged in an equivalent relationship (B / (A + D)> 1: [NCO] / [OH] molar ratio) such that isocyanate groups remain after the reaction.
  • B / (A + D)> 1: [NCO] / [OH] molar ratio 1: [NCO] / [OH] molar ratio
  • the charging ratio is increased, 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 and the curability of the photosensitive resin composition may be affected.
  • the OH group of the alcohol compound (A + D) is 0.1 to 0.9 mol with respect to 1.0 mol of the NCO group of the polyisocyanate compound (B).
  • the first reaction can be carried out without a solvent, but in a solvent having a high viscosity of the product and having no alcoholic hydroxyl group for improving workability or in a polymerizable compound (F) described later. It is preferable to do so.
  • 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 diol compound (A + D) and the polyisocyanate compound (B).
  • the polyurethane compound (E) of the present invention is obtained by reacting (second reaction) a (meth) acrylate compound (C) having at least one hydroxyl group with respect to the remaining isocyanate group after the first reaction. be able to.
  • 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.
  • the second reaction of the present invention is charged in an equivalent relationship such that the isocyanate group of the intermediate obtained after the first reaction is eliminated.
  • the OH group of the (meth) acrylate compound (C) having at least one hydroxyl group is 1.0 to 3.3 mol per 1.0 mol of the NCO group of the intermediate obtained after the first reaction.
  • the amount is 0 mol, more preferably 1.0 to 2.0 mol.
  • the second reaction of the present invention can also be carried out in the absence of a solvent, but in the above-mentioned solvent and / or polymerizable compound (F) described later in the present invention in order to improve workability because the product has a high viscosity. Preferably it is done.
  • 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 is already added to the 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 photosensitive resin composition of the present invention can contain the polyurethane compound (E) of the present invention and a polymerizable compound (F) other than the component (E) as optional components.
  • a polymerizable compound (F) 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 (F-1); urethane (meth) acrylate (F-2). ); Epoxy (meth) acrylate (F-3); (poly) ether (meth) acrylate (F-4); alkyl (meth) acrylate or alkylene (meth) acrylate (F-5); having an aromatic ring (meth) ) Acrylate (F-6); (meth) acrylate (F-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 (F-1) that can be used in combination with the photosensitive resin composition of the present invention is a generic term for (meth) acrylate having one or more ester bonds in the main chain.
  • Acrylate (F-2) is a general term for (meth) acrylate having one or more urethane bonds in the main chain.
  • Epoxy (meth) acrylate (F-3) is a monofunctional or higher functional epoxy compound and (meth).
  • As a general term for (meth) acrylate obtained by reacting acrylic acid, (poly) ether (meth) acrylate (F-4) is a general term for (meth) acrylate having one or more ether bonds in the main chain.
  • Alkyl (meth) acrylate or alkylene (meth) acrylate (F-5) is a linear alkyl, branched alkyl, or halogenated at the end or main chain.
  • (meth) acrylate which may have an atom and / or a hydroxyl group (meth) acrylate (F-6) having an aromatic ring is (meth) acrylate having an aromatic ring in the main chain or side chain.
  • (meth) acrylate (F-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 (F-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 (F-2) that can be used in combination with the photosensitive resin composition of the present invention includes at least one (meth) acryloyloxy group-containing hydroxy compound (F-2-i) and isocyanate compound (F-).
  • hydroxy compound (F-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 (F-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 Compound of 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; , 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.
  • a cyclic skeleton such as tricyclodecane dimethyl
  • the epoxy (meth) acrylate (F-3) that can be used in combination with the photosensitive resin composition of the present invention is obtained by reacting an epoxy resin containing one or more functional epoxy groups with (meth) acrylic acid (meta). ) A general term for acrylate.
  • 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 (F-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.
  • Functional (poly) ether (meth) acrylates include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin-modified butyl ( (Meth) acrylate, dicyclopentenyloxyethyl (meth)
  • 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 compounds such as hydrogenated polybutadiene glycol and other polyhydric hydroxyl compounds and (meth) acrylic Polyfunctional (meth) acrylates derived from acids; 1 mole or more of ethylene oxide, propylene oxide, butylene oxide, etc. per mole 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 (F-5) examples include, for example, 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) acrylics such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • Examples of the (meth) acrylate (F-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 (F-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 thereof 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. However, 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 (F-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 (F-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 (F-10) that can be used in 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 (F) 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 (F-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 (F) is not particularly limited, but the component (F) is 10 to 2000 wt% with respect to 100 wt% of the component (E). %, Preferably 20 to 1000% by weight.
  • the photopolymerization initiator (G) 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 (G) 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 ⁇ -glycidoxypropyl tremethoxysilane 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, light resistance, and optical applications that need to maintain transparency, as well as ink, plastic paint, paper printing, metal coating, furniture It is useful in many fields such as various coating fields such as painting, linings, adhesives, and 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 To a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 manufactured by Nippon Soda Co., Ltd. (iodine value: 12.2, hydroxyl value: 46.8 mg ⁇ KOH) as a hydrogenated polybutadiene polyol compound / G) is 569.73 g (0.24 mol), 7.50 g (0.0024 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g) manufactured by Asahi Glass Co., Ltd. as a diol compound is polymerizable.
  • GI-2000 manufactured by Nippon Soda Co., Ltd.
  • Synthesis example 2 To a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 manufactured by Nippon Soda Co., Ltd. (iodine value: 12.2, hydroxyl value: 46.8 mg ⁇ KOH) as a hydrogenated polybutadiene polyol compound / G) is 545.99 g (0.23 mol), 7.19 g (0.0023 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g) manufactured by Asahi Glass Co., Ltd. as a diol compound is polymerizable.
  • GI-2000 manufactured by Nippon Soda Co., Ltd.
  • Synthesis example 3 In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, as a hydrogenated polybutadiene polyol compound, KRASOL HLBH-P 2000 (iodine value: 13.5, hydroxyl value: 0.89 meq / g) manufactured by CRAY VALLEY 511.69 g (0.23 mol), 7.19 g (0.0023 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g) manufactured by Asahi Glass Co., Ltd.
  • KRASOL HLBH-P 2000 iodine value: 13.5, hydroxyl value: 0.89 meq / g
  • Exenol 3020 polypropylene glycol, hydroxyl value: 35.9 mg ⁇ KOH / g
  • Formulation Example 1 20 parts by mass of the polyurethane compound (E-1) of Synthesis Example 1, 22 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-2000 manufactured by Nippon Soda Co., Ltd.
  • Formulation Example 2 20 parts by mass of the polyurethane compound (E-2) of Synthesis Example 2, 22 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, Yashara Chemical Co., Ltd. Clearon M-105 (aromatically 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
  • LAMBSON speed cure TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) 0.5 parts by mass
  • BASF IRGACURE184 (1-hydroxycyclohexylphenyl) Ketone
  • PBD (2- (4-Bifeni) manufactured by Wako Pure Chemical Industries Lu) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (0.05 parts by mass) was heated to 70 ° C. and mixed to obtain a resin composition of the present invention.
  • the viscosity of the composition was 5000 mPa ⁇ s.
  • Formulation Example 3 20 parts by mass of the polyurethane compound (E-3) of Synthesis Example 3, 22 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-2000 manufactured by Nippon Soda Co., Ltd.
  • Formulation Examples 1 to 3 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 useful as a member for optical applications because it is excellent in flexibility, weather resistance, light resistance, and transparency. 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne : un composé de polyuréthane pouvant donner une composition de résine qui présente une excellente souplesse et une résistance élevée aux intempéries et une résistance élevée à la lumière, qui peut conserver la transparence et qui convient pour une utilisation dans des applications optiques en particulier ; une composition de résine photosensible qui contient le composé ; un procédé pour produire la composition de résine photosensible ; et un produit durci de la composition. Le composé de polyuréthane est obtenu par la réaction d'un composé de polybutadiènepolyol hydrogéné (A), d'un composé de polyisocyanate (B), d'un composé de (méth)acrylate (C) présentant un groupe hydroxyle et, comme constituant facultatif, d'un composé de diol (D) autre que le composé (A).
PCT/JP2014/082128 2013-12-05 2014-12-04 Composé de polyuréthane, composition de résine photosensible, procédé pour produire une composition de résine photosensible et produit durci WO2015083795A1 (fr)

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CN112143445A (zh) * 2019-06-27 2020-12-29 博斯蒂克股份公司 基于聚氨酯/羟基化(甲基)丙烯酸系单体的热熔压敏粘合剂组合物
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JP6878080B2 (ja) * 2017-03-27 2021-05-26 セーレン株式会社 インクジェットインクおよびプリント物の製造方法
CN113845623A (zh) * 2021-09-28 2021-12-28 泉州师范学院 一种用于光固化3d打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物及其制备方法

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JPWO2015190560A1 (ja) * 2014-06-11 2017-04-20 日本化薬株式会社 タッチパネル用紫外線硬化型接着剤組成物及び物品
WO2016039324A1 (fr) * 2014-09-12 2016-03-17 日本化薬株式会社 Composition de résine, composition de résine polymérisable, composition de résine photosensible, et produit durci de celles-ci
JP2016056321A (ja) * 2014-09-12 2016-04-21 日本化薬株式会社 樹脂組成物
AU2019225884B2 (en) * 2018-02-22 2024-02-15 Basf Se Polyurethane-based polymer material having excellent resistance to heat distortion and elongation at tear
US12037445B2 (en) * 2018-02-22 2024-07-16 Basf Se Polyurethane-based polymer material having excellent resistance to heat distortion and elongation at tear
CN112143445A (zh) * 2019-06-27 2020-12-29 博斯蒂克股份公司 基于聚氨酯/羟基化(甲基)丙烯酸系单体的热熔压敏粘合剂组合物
EP3757144A1 (fr) * 2019-06-27 2020-12-30 Bostik SA Composition adhésive thermofusible sensible à la pression à base de polyuréthane-(méth)acrylique
US20200407601A1 (en) * 2019-06-27 2020-12-31 Bostik Sa Hot-melt pressure-sensitive adhesive composition based on polyurethane/(meth)acrylic
FR3097869A1 (fr) * 2019-06-27 2021-01-01 Bostik Sa Composition adhésive thermofusible sensible à la pression à base de polyuréthane-(méth)acrylique
US11873429B2 (en) 2019-06-27 2024-01-16 Bostik Sa Hot-melt pressure-sensitive adhesive composition based on polyurethane/(meth)acrylic
CN112143445B (zh) * 2019-06-27 2024-05-14 博斯蒂克股份公司 基于聚氨酯/羟基化(甲基)丙烯酸系单体的热熔压敏粘合剂组合物

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