WO2018169031A1 - Polymère de (méth)acrylate d'uréthanne - Google Patents

Polymère de (méth)acrylate d'uréthanne Download PDF

Info

Publication number
WO2018169031A1
WO2018169031A1 PCT/JP2018/010385 JP2018010385W WO2018169031A1 WO 2018169031 A1 WO2018169031 A1 WO 2018169031A1 JP 2018010385 W JP2018010385 W JP 2018010385W WO 2018169031 A1 WO2018169031 A1 WO 2018169031A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
group
urethane
acrylate
curable composition
Prior art date
Application number
PCT/JP2018/010385
Other languages
English (en)
Japanese (ja)
Inventor
健太郎 内野
葉山　康司
Original Assignee
三菱ケミカル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to CN201880018434.0A priority Critical patent/CN110446736B/zh
Priority to JP2019506283A priority patent/JPWO2018169031A1/ja
Priority to KR1020197027883A priority patent/KR102275295B1/ko
Publication of WO2018169031A1 publication Critical patent/WO2018169031A1/fr
Priority to JP2022108317A priority patent/JP2022133387A/ja

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
    • C08G18/678—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a urethane (meth) acrylate polymer excellent in transparency, weather resistance, and scratch resistance after coating and curing a curable composition on a substrate, and a curable composition containing the same. Moreover, this invention relates to the hardened
  • the radical polymerization type curable composition can be cured in a short time by irradiation with active energy rays, and can provide a film or a molded product excellent in chemical resistance, scratch resistance, weather resistance, heat resistance, etc. Therefore, it is used in coating compositions for coating the surfaces of automobiles, home appliances, woodwork products, plastic molded products, transfer materials and the like.
  • Patent Document 1 discloses a coating composition in which a bisbenzotriazolylphenol compound is added as an ultraviolet absorber.
  • Patent Document 2 discloses a coating composition in which a UV absorber having a specific structure is incorporated into a polymer skeleton.
  • Patent Document 3 discloses a curable resin composition in which a bisbenzotriazolylphenol ultraviolet absorber is incorporated into a polymer skeleton via an ester bond.
  • the coating composition described in Patent Document 1 since the ultraviolet absorber is not incorporated in the polymer skeleton, the transparency and weather resistance of the coating film are caused by bleeding out of the ultraviolet absorber from the coating film. Was insufficient.
  • the coating composition described in Patent Document 2 has insufficient weather resistance since the ultraviolet absorbing performance of the ultraviolet absorber is not sufficient. Since the curable composition described in Patent Document 3 incorporates an ultraviolet absorber into the polymer skeleton via an ester bond, hydrolysis resulting from the ester bond occurs, and the ultraviolet absorber bleeds out. The weather resistance was insufficient.
  • the present invention solves the above-described problems, and includes a urethane (meth) acrylate polymer that prevents bleeding out of an ultraviolet absorber and provides a coating film excellent in weather resistance, scratch resistance, and transparency, and the same.
  • the object is to provide a curable composition.
  • a urethane (meth) acrylate polymer having a chemical structure represented by the following formula (1) [In the formula, A represents a single bond or an optionally substituted methylene group, alkylene group, —O— group, —NH— group, —S— group, —SO— group or —SO 2 — group.
  • R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom.
  • R 5 and R 6 independently represent an alkylene group, an alkoxylene group, or an arylene group.
  • X 1 has the same meaning as X 1 in the formula (3).
  • [5] The urethane (meth) acrylate polymer according to any one of [1] to [4], which has a weight average molecular weight (Mw) of 500 to 30,000.
  • Mw weight average molecular weight
  • [6] The urethane (meth) according to any one of [1] to [5], wherein the ratio of the chemical structure represented by the formula (1) in the urethane (meth) acrylate polymer is 5 to 60% by weight.
  • Acrylate polymer [7]
  • a curable composition comprising the urethane (meth) acrylate polymer according to any one of [1] to [6] and an organic solvent.
  • a headlamp lens having a cured product of the curable composition according to [11] on a substrate.
  • a glazing material having a cured product of the curable composition according to [11] on a substrate.
  • a decorative film having a cured product of the curable composition according to [11] on a substrate.
  • a step of applying the urethane (meth) acrylate polymer according to any one of [1] to [6] or the curable composition according to any one of [7] to [10] on a substrate The manufacturing method of a film including the process of irradiating an active energy ray to the said urethane (meth) acrylate polymer or the said curable composition, obtaining the laminated body which has hardened
  • a method for producing a urethane (meth) acrylate polymer in which the following compound (A) and the following compound (B) are reacted to obtain a urethane polymer precursor, and then the following compound (C) is reacted therewith.
  • R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom.
  • R 5 and R 6 independently represent an alkylene group, an alkoxylene group, or an arylene group.
  • Compound (C) Compound [18] having hydroxyl group and (meth) acryloyl group [18]
  • compound (D) was reacted to obtain a urethane polymer precursor, The method for producing a urethane (meth) acrylate polymer according to [17], wherein the compound (C) is reacted.
  • Compound (D) aliphatic polyol having a molecular weight of 500 or less
  • the urethane (meth) acrylate polymer which prevents the bleeding out of a ultraviolet absorber, and the coating film excellent in a weather resistance, an abrasion resistance, and transparency is obtained, and a curable composition containing this are obtained.
  • the laminated body and decorating film which have the layer which consists of the said hardened
  • (meth) acrylate is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The same applies to “(meth) acryloyl” and “(meth) acryl”. It is.
  • the urethane (meth) acrylate polymer of the present invention has a chemical structure represented by the following formula (1).
  • A is a single bond or may have a substituent, a methylene group, an alkylene group, an —O— group, an —NH— group, an —S— group, an —SO— group, or —SO 2. It may be any group. From the viewpoint of transparency of the cured product containing the urethane (meth) acrylate polymer of the present invention and prevention of bleeding out of the cured product of the ultraviolet absorbent, a methylene group and an alkylene group are preferable, and a methylene group is more preferable.
  • R 1 , R 2 , R 3 and R 4 may independently be any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom.
  • a hydrogen atom, an alkyl group, or an alkoxy group is preferable from the viewpoint of preventing transparency of the cured product of the urethane (meth) acrylate polymer or curable composition of the present invention and bleeding out from the cured product of the bisbenzotriazolylphenol skeleton. .
  • R 5 and R 6 are the same or different and may be any one of an alkylene group, an alkoxylene group, and an arylene group.
  • An alkylene group and a methylene group are preferred from the viewpoint of transparency of the cured product of the urethane (meth) acrylate polymer or curable composition of the present invention and prevention of bleeding out from the cured product of the bisbenzotriazolylphenol skeleton.
  • a bisbenzotriazolylphenol skeleton that acts as an ultraviolet absorber is incorporated into the molecular chain of the polymer via a chemically stable urethane bond. Since the bisbenzotriazolylphenol skeleton has a structure in which benzotriazolylphenol is dimerized, it has a high ultraviolet-absorbing ability per unit weight and can impart high weather resistance even in a small amount. Furthermore, in the present invention, since the bisbenzotriazolylphenol skeleton is incorporated through a urethane bond, the bisbenzotriazolylphenol skeleton is difficult to bleed out due to hydrolysis or the like, so that it has long-term weather resistance. Also excellent.
  • the chemical structure represented by (1) is preferably a chemical structure represented by the following formula (2).
  • the ratio of the chemical structure represented by the formula (1) in the urethane (meth) acrylate polymer of the present invention is preferably 5% by weight or more, 20% by weight or more is more preferable. Moreover, 60 weight% or less is preferable and 35 weight% or less is more preferable.
  • the urethane (meth) acrylate polymer of the present invention preferably has a chemical structure represented by the following formula (3).
  • the urethane (meth) acrylate polymer of the present invention has a chemical structure represented by the following formula (4-1) and a chemical structure represented by the following formula (4-2) as the chemical structure represented by the formula (3). By including at least one of the structures, the transparency of the cured product can be improved.
  • a urethane (meth) acrylate polymer having a bisbenzotriazolylphenol skeleton is used as a curable composition
  • urethane (meth) acrylate The solubility of the polymer in an organic solvent can be improved.
  • X 1 is not particularly limited as long as it is an aliphatic structure having a molecular weight of 500 or less, but is preferably an aliphatic structure having a molecular weight of 400 or less, more preferably an aliphatic structure having a molecular weight of 300 or less. .
  • X 1 is preferably an aliphatic structure having a molecular weight of 14 or more, more preferably an aliphatic structure having 28 or more.
  • X 1 corresponds to a residue from which a hydroxyl group is bonded to the aliphatic structure of the compound (B) described later, and is a linear aliphatic structure or a branched aliphatic structure. It may be a cyclic structure.
  • n is an integer of 2 to 8, but n is preferably 2 to 6, and more preferably 2 to 4.
  • the urethane (meth) acrylate polymer of the present invention has a chemical structure represented by the following formula (4-1) and a chemical structure represented by the following formula (4-2) as the chemical structure represented by the formula (3). It is preferable to include at least one of the structures.
  • (Formula (4-1), (4-2) in, X 1 has the same meaning as X 1 in the formula (3).)
  • the urethane (meth) acrylate polymer of the present invention contains a structural unit derived from a compound having a hydroxyl group and a (meth) acryloyl group.
  • the compound having a hydroxyl group and a (meth) acryloyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate.
  • Cyclohexanedimethanol mono (meth) acrylate addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, addition reaction product of 4-hydroxybutyl (meth) acrylate and caprolactone, bisphenol A diglycidyl ether diacrylate, Glycol mono (meth) acrylate, glycerin (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) a Relate, dipentaerythritol penta (meth) acrylate.
  • Weight average molecular weight (Mw)] 500 or more are preferable and, as for the weight average molecular weight (Mw) of the urethane (meth) acrylate polymer of this invention, 10,000 or more are more preferable. Moreover, 30,000 or less is preferable and 20,000 or less is more preferable. When the weight average molecular weight of the urethane (meth) acrylate polymer is in the above range, the transparency of the urethane (meth) acrylate polymer or the curable composition in the solution state and the scratch resistance of the cured film are improved.
  • the said weight average molecular weight was measured by the method shown in an Example by the gel permeation chromatography measurement (GPC measurement).
  • the urethane (meth) acrylate polymer of the present invention is obtained by reacting the following compound (A) and the following compound (B) to obtain a precursor of a urethane polymer, and then reacting the following compound (C) with this. can get.
  • R 1, R 2, R 3 and R 4 independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom.
  • R 5 and R 6 independently represent an alkylene group, an alkoxylene group, or an arylene group.
  • Compound (C) Compound having a hydroxyl group and a (meth) acryloyl group
  • the urethane (meth) acrylate polymer of the present invention is reacted with a polyol other than the compound (B) to obtain a urethane polymer precursor, and then the compound ( C) may be reacted.
  • polyols other than the compound (B) examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, etc.
  • two or more active hydrogen which reacts with an isocyanate group is used as a chain extension agent. You may add the compound which has.
  • Examples of the polyisocyanate of the compound (A) include chain aliphatic polyisocyanate, aromatic polyisocyanate, and alicyclic polyisocyanate. Among these, a chain alicyclic polyisocyanate is preferable from the viewpoint of enhancing the weather resistance and hardness of the cured product obtained.
  • chain aliphatic polyisocyanate examples include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate, and aliphatic triisocyanates such as tris (isocyanatohexyl) isocyanurate.
  • aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate
  • aliphatic triisocyanates such as tris (isocyanatohexyl) isocyanurate.
  • aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate
  • aromatic polyisocyanate examples include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and naphthalene diisocyanate.
  • aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and naphthalene diisocyanate.
  • Tolylene diisocyanate and diphenylmethane diisocyanate are preferable as the aromatic polyisocyanate from the viewpoint of increasing the mechanical strength of the urethane (meth) acrylate polymer or the cured film of the curable composition. These may be used alone or in combination of two or more.
  • polyisocyanate having an alicyclic structure examples include diisocyanates having an alicyclic structure such as bis (isocyanate methyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate, and tris (isocyanate isophorone) isocyanurate. And triisocyanate having an alicyclic structure.
  • the alicyclic polyisocyanate is preferably isophorone diisocyanate. These may be used alone or in combination of two or more.
  • the alicyclic structure preferably has 5 or more carbon atoms, more preferably 6 or more carbon atoms. Moreover, carbon number 15 or less is preferable and carbon number 13 or less is more preferable. Furthermore, the alicyclic structure is preferably a cycloalkylene group. As the compound (A), one type may be used, or two or more types may be used.
  • the compound (A) is preferably 5% by weight or more, and more preferably 25% by weight or more in the urethane (meth) acrylate polymer of the invention from the viewpoint of the transparency, weather resistance and scratch resistance of the cured product. Moreover, 60 weight% or less is preferable and 50 weight% or less is more preferable from the point which is excellent in transparency, a weather resistance, and scratch resistance of hardened
  • the compound (B) is a polyol represented by the following formula (5).
  • A represents a single bond or an optionally substituted methylene group, alkylene group, —O— group, —NH— group, —S— group, —SO— group or —SO 2 — group.
  • R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom.
  • R 5 and R 6 independently represent an alkylene group, an alkoxylene group, or an arylene group.
  • the compound (B) represented by the formula (5) is preferably a polyol represented by the following formula (10).
  • the ratio of the chemical structure represented by the formula (5) in the urethane (meth) acrylate polymer of the present invention is preferably 5% by weight or more, 20% by weight or more is more preferable. Moreover, 60 weight% or less is preferable and 35 weight% or less is more preferable.
  • Dinesorb T-33 manufactured by Daiwa Kasei Co., Ltd. can be used as a commercially available product.
  • the compound (B) is preferably 5% by weight or more, more preferably 25% by weight or more based on the total polyol component used as a raw material for the urethane (meth) acrylate polymer. More preferred. Moreover, 95 weight% or less is preferable and 90 weight% or less is more preferable from the point which is excellent in transparency in a solution state, transparency of a cured film, and abrasion resistance.
  • Examples of the compound (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and cyclohexanedimethanol mono (Meth) acrylate, addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, addition reaction product of 4-hydroxybutyl (meth) acrylate and caprolactone, bisphenol A diglycidyl ether diacrylate, mono (meta) of glycol ) Acrylate, glycerin (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Rupenta (meth) acrylate and the like can be mentioned.
  • 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 from the viewpoint of improving the mechanical strength of the resulting cured film and the curability of the urethane (meth) acrylate polymer -Hydroxybutyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are preferable.
  • an epoxy (meth) acrylate having a chain aliphatic structure having 2 to 12 carbon atoms can be used as the compound (C).
  • the raw material for synthesizing the epoxy (meth) acrylate include ethylene glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,5-pentanediol diglycidyl ether.
  • the epoxy compound includes 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diester.
  • Epoxy compounds having a chain aliphatic structure having 4 to 6 carbon atoms such as glycidyl ether are preferred.
  • the compound (C) can be obtained by subjecting the epoxy compound to a ring-opening addition reaction with a compound having a (meth) acryloyl group and a carboxyl group.
  • a compound having a (meth) acryloyl group and a carboxyl group a compound having a (meth) acryloyl group and a carboxyl group can be used.
  • Examples of the compound include (meth) acrylic acid; carboxyalkyl (meth) acrylate such as carboxymethyl (meth) acrylate, carboxyethyl (meth) acrylate, carboxypropyl (meth) acrylate, and carboxypropyl (meth) acrylate; Reaction products of hydroxyalkyl (meth) acrylates such as ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and carboxylic anhydrides such as phthalic anhydride, succinic anhydride, maleic anhydride, etc. Is mentioned. These may be used alone or in combination of two or more.
  • acrylic acid is preferable as the compound having a (meth) acryloyl group and a carboxyl group from the viewpoint of curability of the urethane (meth) acrylate polymer.
  • Examples of the epoxy (meth) acrylate of the compound (C) include Kayrad (registered trademark) R-167 (manufactured by Nippon Kayaku Co., Ltd.), NK oligo EA-5520, EA-5321 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like. It is done.
  • the compound (C) one type may be used, or two or more types may be used.
  • the compound (C) is used as a raw material for the urethane (meth) acrylate polymer from the viewpoint of further improving the scratch resistance of the cured film of the curable composition of the present invention and obtaining good stretchability after curing.
  • the total polyol component is preferably 4% by weight or more, more preferably 8% by weight or more. Moreover, 25 weight% or less is preferable and 18 weight% or less is more preferable.
  • the compound (D) is an aliphatic polyol having a molecular weight of 500 or less.
  • Examples of the compound (D) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Linear fat such as octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, etc.
  • Diols having a family structure propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-pentane Branched chain such as diol, 3-methyl-1,5-pentanediol, 1,8-nonanediol Diols having an aliphatic structure; compounds having a branched aliphatic structure such as trimethylolpropane, glycerin, sorbitol, mannitol, pentaerythritol and three or more hydroxyl groups bonded thereto; cyclopropanediol, cyclohexanediol, cyclohexanedi Examples include diols having an alicyclic structure such as methanol, hydrogenated bisphenol A, tricyclodecanediol
  • those having a linear aliphatic structure are preferred from the viewpoint of excellent scratch resistance of the cured film, and particularly at least one selected from ethylene glycol, 1,4-butanediol, and 1,12-dodecanediol. It is preferable to use one. Among these, ethylene glycol is preferable from the viewpoint of chemical resistance, and 1,12-dodecanediol is preferable from the viewpoint of scratch resistance and flexibility. In order to further improve the weather resistance of the cured film, it is necessary to introduce more compound (B) into the urethane (meth) acrylate polymer. For this purpose, the compound (D) preferably contains a diol having a branched aliphatic structure.
  • the diol having a branched aliphatic structure propylene glycol, 1,3-butanediol, neopentyl glycol, 3-methyl-1,5 can be complemented with the solution transparency and the low solubility of the ultraviolet absorption skeleton.
  • -Pentanediol and the like are more preferable, and 1,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol and the like are more preferable.
  • the compound (D) one type may be used, or two or more types may be used.
  • the compound (D) is based on the total polyol component used as a raw material for the urethane (meth) acrylate polymer. It is preferably 3% by weight or more, and more preferably 10% by weight or more.
  • a compound (D) is 99 with respect to all the polyol components used as a raw material of a urethane (meth) acrylate polymer. .95% by weight or less is preferable, and 90% by weight or less is more preferable.
  • polyols other than the compound (B) and the compound (D) examples include aromatic polyols having a molecular weight of 500 or less, and high molecular weight polyols having a molecular weight exceeding 500.
  • polyol having an aromatic structure having a molecular weight of 500 or less examples include bishydroxyethoxybenzene, bishydroxyethyl terephthalate, and bisphenol A. These may be used alone or in combination of two or more.
  • Examples of the high molecular weight polyol having a molecular weight exceeding 500 include polyether polyol, polyester polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol, and silicon polyol. These may be used alone or in combination of two or more.
  • polycarbonate polyol When using the high molecular weight polyol, polycarbonate polyol is preferable.
  • the polycarbonate polyol can be obtained, for example, by reacting at least one carbonate compound selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate with at least one of diols and polyether polyols.
  • diols examples include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, diethylene glycol, dipropylene glycol, polybutadiene diol and the like.
  • Polycarbonate polyol can be obtained as a commercial product.
  • commercially available products include DURANOL (registered trademark) T4671 (manufactured by Asahi Kasei Co., Ltd.), DURANOL (registered trademark) T4691 (manufactured by Asahi Kasei Co., Ltd.), DURANOL (registered trademark) 5651 (manufactured by Asahi Kasei Corporation), and DURANOL (registered trademark) 6001 (registered trademark). Asahi Kasei Co., Ltd.).
  • chain extender examples include low molecular weight diamine compounds having a number average molecular weight of 500 or less, and examples include aromatic compounds such as 2,4- or 2,6-tolylenediamine, xylylenediamine, and 4,4′-diphenylmethanediamine.
  • Group diamine ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 2,2,4- or Aliphatic diamines such as 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4′-dicyclohexylmeta Diamine, isopropylidene cyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3-bis-aminomethyl cyclohexane, alicyclic diamines such as tricyclodecane diamine. These may be used alone or in combination of two or more.
  • the usage-amount of all the polyols is 70 mol% with respect to the total usage-amount of the compound which combined the compound (B) and the compound (C), and other polyol components and chain extension agents.
  • the above is preferable, and 95 mol% or more is more preferable.
  • a polyol other than the compound (B) and the compound (B) is reacted under a condition that the isocyanate group becomes excessive to obtain a precursor of a urethane polymer having an isocyanate terminal, It is preferable to react the urethane polymer precursor having an isocyanate terminal with the compound (C).
  • the compound (C) when the compound (C) has two or more hydroxyl groups, the compound (C) is preferably used in an excess amount with respect to all isocyanate groups of the urethane (meth) acrylate polymer.
  • the total amount of the compound containing a functional group that reacts with an isocyanate group in the compound (C) and other raw materials is preferably 2 mol% or more, more preferably 10 mol% or more. Moreover, 70 mol% or less is preferable and 50 mol% or less is more preferable.
  • an organic solvent can be used for the purpose of adjusting the viscosity.
  • the organic solvent any known organic solvent can be used as long as the effects of the present invention are obtained.
  • Preferred organic solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, dimethylformamide and the like.
  • the said organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • the said organic solvent can be normally used at 300 weight% or less with respect to the total mass of a urethane (meth) acrylate polymer.
  • a catalyst can be used for the urethanization reaction.
  • the catalyst include tin-based catalysts such as dibutyltin laurate, dibutyltin dioctate, dioctyltin dilaurate, and dioctyltin dioctate; and bismuth-based catalysts such as bismuth tris (2-ethylhexanoate).
  • tin-based catalysts such as dibutyltin laurate, dibutyltin dioctate, dioctyltin dilaurate, and dioctyltin dioctate
  • bismuth-based catalysts such as bismuth tris (2-ethylhexanoate.
  • dioctyltin dilaurate and bismuth tris (2-ethylhexanoate) are preferable from the viewpoint of environmental adaptability, catalytic activity, storage stability, and the like.
  • a catalyst may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the amount of the catalyst used is preferably 2,000 ppm or less, more preferably 1,000 ppm or less, based on the total amount of raw materials charged. Moreover, 10 ppm or more is preferable and 30 ppm or more is more preferable.
  • a polymerization inhibitor in combination with the production of the urethane (meth) acrylate polymer.
  • the polymerization inhibitor include phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, and dibutylhydroxytoluene, amines such as phenothiazine and diphenylamine, copper salts such as copper dibutyldithiocarbamate, and manganese salts such as manganese acetate. , Nitro compounds, nitroso compounds and the like.
  • the polymerization inhibitor is preferably a phenol.
  • the said polymerization inhibitor may be used individually by 1 type, and may mix and use 2 or more types.
  • the amount of the polymerization inhibitor used is preferably 3,000 ppm or less, more preferably 1,000 ppm or less, based on the total amount of raw materials charged. Moreover, 50 ppm or more is preferable and 100 ppm or more is more preferable.
  • the reaction temperature of the urethanization reaction is preferably 20 ° C. or higher and more preferably 40 ° C. or higher from the viewpoint of increasing the reaction rate and improving the production efficiency.
  • the reaction temperature is preferably 120 ° C. or less, more preferably 100 ° C. or less from the viewpoint that side reactions such as allophanatization reaction do not easily occur.
  • reaction temperature is below the boiling point of the organic solvent.
  • the reaction time is usually 5 to 20 hours.
  • the curable composition of the present invention preferably contains the urethane (meth) acrylate polymer and an organic solvent.
  • the content of the urethane (meth) acrylate polymer is preferably 40% by weight or more based on the total amount of all components (solid content) excluding the organic solvent in the curable composition. More preferably, it is more than wt%.
  • the upper limit of content of a urethane (meth) acrylate polymer is 100 weight%. It is preferable for the content of the urethane (meth) acrylate polymer to be in the above range since the curing rate and surface curability of the curable composition will be good and no tack will remain.
  • the structural ratio of the compound represented by the formula (1) in the polymerization component of the curable composition is preferably 10% by weight or more from the viewpoint of excellent transparency, weather resistance and scratch resistance of the cured product. Moreover, 25 weight% or less is preferable.
  • the polymerization component of the curable composition is a component having an unsaturated double bond that is polymerizable with respect to active energy rays, and is a urethane (meth) acrylate polymer contained in the curable composition, active energy. It means a line curable polymer and an active energy ray reactive monomer.
  • the organic solvent can be used for adjusting the viscosity of the coating material when forming the coating film of the curable composition of the present invention.
  • the solid content concentration of the curable composition is preferably 5 to 90 wt. 10 weight% or more is preferable and 15 weight% or more is more preferable. Moreover, 80 weight% or less is preferable and 60 weight% or less is more preferable.
  • the solubility parameter of the organic solvent (hereinafter referred to as “SP value”) is preferably 8.0 or more from the viewpoint of the solubility of the urethane (meth) acrylate polymer, and 11.5 from the viewpoint of the transparency of the solution. The following is preferred.
  • the organic solvent examples include toluene (SP value: 9.1), xylene (SP value: 9.1), ethyl acetate (SP value: 8.7), butyl acetate (SP value: 8.7), Cyclohexanone (SP value: 9.8), methyl ethyl ketone (SP value: 9.0), methyl isobutyl ketone (SP value: 8.7), N-methylpyrrolidone (SP value: 11.2), isopropyl alcohol (SP value) : 11.5).
  • the SP value is calculated by the method proposed by Fedors et al.
  • SP value means the value as a mixture, when using a mixed solvent.
  • the curable composition of the present invention includes, as other components, an active energy ray reactive monomer, an active energy ray curable polymer (excluding the urethane (meth) acrylate polymer of the present invention), a polymerization initiator, and a photosensitizer. Sensitizers, epoxy compounds and other additives may also be included.
  • any known active energy ray-reactive monomer can be used as the active energy ray-reactive monomer as long as the effects of the present invention are obtained.
  • These active energy ray reactive monomers adjust the physical properties such as the hydrophilicity / hydrophobicity of the urethane (meth) acrylate polymer of the present invention, the hardness of the cured product when the resulting composition is cured, and the elongation of the cured product.
  • Used for purposes such as An active energy ray reactive monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • Examples of the active energy ray-reactive monomer include vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specific examples include styrene, ⁇ -methylstyrene, ⁇ -chlorostyrene, and vinyl.
  • Aromatic vinyl monomers such as toluene and divinylbenzene; vinyl ester monomers such as vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and divinyl adipate
  • Vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether
  • allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether and allyl glycidyl ether; (meth) acrylamide, N, N-dimethylacrylamide, N , N-dimethylmethacrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (meth) acryloylmorpholine, methylenebis (Meth)
  • Molecules such as trimethylcyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, etc.
  • a monofunctional (meth) acrylate having a ring structure therein is preferred.
  • the active energy ray reactivity with respect to the total amount of all components (solid content) excluding the organic solvent of the curable composition is preferably 50% by weight or less, and more preferably 30% by weight or less.
  • Examples of the active energy ray-curable polymer include epoxy (meth) acrylate polymers, acrylic (meth) acrylate polymers, polyester (meth) acrylate polymers, polycarbonate (meth) acrylate polymers, polybutadiene (meth ) Acrylate polymer, polyether (meth) acrylate (excluding those described in the active energy ray-reactive monomer).
  • the active energy ray-curable polymer may be used alone or in combination of two or more.
  • the polymerization initiator is mainly used for the purpose of improving the polymerization efficiency of a polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams.
  • active energy rays such as ultraviolet rays and electron beams.
  • any known radical photopolymerization initiator can be used as long as the effects of the present invention are obtained.
  • a polymerization initiator may be used individually by 1 type, and 2 or more types may be mixed and used for it. Furthermore, you may use together radical photopolymerization initiator and a photosensitizer.
  • radical photopolymerization initiator examples include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methylorthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chloro Thioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl benzoyl formate, 2-methyl-1- [4- Methylthio) phenyl] -2-
  • -Trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl 2-methyl-propan-1-one is more preferred.
  • a photocationic polymerization initiator is included as a polymerization initiator together with the photoradical polymerization initiator. It may be. A well-known thing can be used for a photocationic polymerization initiator in the range which does not inhibit the effect of this invention remarkably.
  • the content of the polymerization initiator is preferably 10% by weight or less, based on the total weight of the polymerization components of the curable composition, because the mechanical strength is not easily lowered by the initiator decomposition product. The following is more preferable.
  • the photosensitizer can be used for the same purpose as the polymerization initiator.
  • examples of the photosensitizer include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4 -Dimethylaminoacetophenone and the like.
  • a photosensitizer may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the content of the photosensitizer is 10 with respect to the total weight of the polymerization component of the curable composition, since the mechanical strength is not easily lowered due to the reduction of the crosslinking density. % By weight or less is preferable, and 5% by weight or less is more preferable.
  • the additive examples include silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, talc, kaolin, metal oxide, metal fiber, iron, lead, metal powder and other fillers; carbon fiber, carbon black , Graphite, carbon nanotubes, carbon materials such as C60 fullerenes; antioxidants, heat stabilizers, UV absorbers, hindered amine light stabilizers (HALS), surface hydrophilizing agents, antistatic agents, slipperiness imparting agents Modifiers such as plasticizers, mold release agents, antifoaming agents, leveling agents, anti-settling agents, surfactants, thixotropy imparting agents, flame retardants, flame retardant aids, polymerization inhibitors, silane coupling agents; Examples thereof include colorants such as pigments, dyes, and hue adjusting agents.
  • the said additive may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • the content of the additive is 10% by weight with respect to the total weight of the polymerization component of the curable composition, because the mechanical strength is not easily lowered due to the reduced crosslinking density.
  • the following is preferable, and 5% by weight or less is more preferable.
  • the method of adding the additive to the curable composition of the present invention is not particularly limited, and examples thereof include conventionally known mixing and dispersing methods.
  • the processing method include a stirrer, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, a kneader, a homogenizer, and an ultrasonic disperser.
  • the viscosity of the curable composition of the present invention is preferably 5 mPa ⁇ s or more, and more preferably 10 mPa ⁇ s or more from the viewpoints of handleability, coatability, moldability, and three-dimensional formability. Further, it is preferably 50,000 mPa ⁇ s or less, and more preferably 10,000 mPa ⁇ s or less.
  • the viscosity of the curable composition can be adjusted by, for example, the content of the urethane (meth) acrylate polymer according to the present invention, the type of the additive, the blending ratio thereof, and the like. The viscosity was measured at 25 ° C. in an E-type viscometer (rotor 1 ° 34 ′ ⁇ R24).
  • a coating method of the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention a bar coater method, an applicator method, a curtain flow coater method, a roll coater method, a spray method, a gravure coater method, a comma coater Method, reverse roll coater method, lip coater method, die coater method, slot die coater method, air knife coater method, dip coater method, etc., among which the bar coater method and the gravure coater method are applicable.
  • the urethane (meth) acrylate polymer of the present invention can be used alone by the coating method.
  • Examples of the substrate on which the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention is applied include, for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyolefins such as polypropylene and polyethylene; Examples include various plastics such as polycarbonate and (meth) acrylic polymers, glass, and metals. Among these, polyethylene terephthalate is preferable. Moreover, about the shape of these base materials, even if it is flat things, such as a film form and a sheet form, and what was shape
  • the hardened product / Laminate is obtained by irradiating an active energy ray to the urethane (meth) acrylate polymer of this invention, or the curable composition of this invention.
  • the active energy rays include infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays. From the viewpoint of apparatus cost and productivity, it is preferable to use an electron beam or ultraviolet rays.
  • Light sources include electron beam irradiation equipment, ultra high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, Ar laser, He-Cd laser, solid state laser, xenon lamp, high frequency induction mercury lamp, solar Light or the like can be used.
  • the irradiation amount of the active energy ray can be appropriately selected according to the type of the active energy ray.
  • the irradiation amount is preferably 1 to 15 Mrad.
  • the irradiation amount is preferably 50 to 1,500 mJ / cm 2 .
  • the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention may be in any atmosphere of air, an inert gas such as nitrogen or argon. Moreover, you may irradiate in the sealed space between a film or glass, and a metal metal mold
  • the thickness of the cured product is appropriately determined according to the intended use, but the thickness of the cured product is preferably 1 ⁇ m or more from the viewpoint of good design and functional expression after three-dimensional processing, 2 ⁇ m or more is preferable. In addition, the thickness of the cured product is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 20 ⁇ m or less from the viewpoint of good curability and three-dimensional processability.
  • the laminate of the present invention can be obtained by curing the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention on a substrate.
  • the laminate of the present invention may have a layer other than the cured product of the present invention between the substrate and the cured product of the present invention, or may be disposed outside the laminate of the present invention.
  • the said laminated body may have multiple layers of the base material and the hardened
  • a method of obtaining a laminate having a multi-layered cured product all layers are laminated in an uncured state and then cured with active energy rays, and the lower layer is cured with active energy rays or semi-cured.
  • a known method such as a method of applying an upper layer and curing again with active energy rays, a method of bonding each layer to an uncured state or a semi-cured state after applying each layer to a substrate can be applied. From the viewpoint of improving the adhesion between layers, a method of curing with active energy rays after laminating in an uncured state is preferable.
  • a known method such as sequential coating in which the upper layer is applied after the lower layer is applied or simultaneous multilayer coating in which two or more layers are simultaneously applied from multiple slits is applied. Yes, but not necessarily.
  • the laminate of the present invention can be suitably used as a coating substitute film.
  • the present invention can be effectively applied to interior and exterior building materials and various members such as automobiles, home appliances, and information electronic materials.
  • the laminated body of the present invention is suitable for a glazing member or a decorative film from the viewpoint that the weather resistance, bleed-out resistance, and scratch resistance necessary for surface protection can be imparted in a single layer and the process is simple. used.
  • the decorative film is a film to which irregularities such as wood grain, metal tone, embossing, various designs, designs such as characters, and decoration are added by printing, painting, vapor deposition, coloring, and the like.
  • the molded article formed by applying the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention to the surface of a molded article such as polycarbonate and irradiating an active energy ray is an automobile head. It is suitably used for lamp lenses and automotive polymer glass.
  • the laminate of the present invention can be stretched and used as a film.
  • the method for producing the film includes a step of applying the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention on a substrate, and irradiating the curable composition with active energy rays to form a cured product. It is preferable to include the process of obtaining the laminated body which has, and the process of extending
  • the step of applying the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention on a substrate and the urethane (meth) acrylate polymer or the curable composition are active.
  • Each of the steps of obtaining a cured product by irradiating energy rays can be performed under the above-described conditions.
  • the step of stretching the cured product can be usually performed by heating at 60 to 200 ° C., preferably 100 to 180 ° C.
  • molding method of a decorating film well-known methods, such as insert molding, in-mold shaping
  • the urethane (meth) acrylate polymer and the cured film were evaluated by the following methods. ⁇ Molecular weight> Using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation), tetrahydrofuran (THF) as a solvent, polystyrene as a standard sample, TSKgel superH1000 + H2000 + H3000 as a column, a liquid feeding speed of 0.5 mL / min, and a column oven temperature of 40 ° C. The weight average molecular weight Mw and the number average molecular weight Mn of the urethane (meth) acrylate polymer were measured.
  • the appearance of the coating film on the obtained laminate was visually confirmed to be transparent or cloudy, and the haze value H was measured.
  • the haze value H was measured according to JIS K7105 by using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory Co., Ltd.).
  • the color tone b 0 of the coating film on the obtained laminate was measured using a spectrocolorimeter (manufactured by Konica Minolta, product name “Spectrophotometer CM-5”).
  • a metal weather meter product name “Daipura Metal Weather KU-R4Ci-W” manufactured by Daipura Wintes Co., Ltd.
  • the accelerated weathering test was conducted for 168 hours (14 cycles) and 336 hours (28 cycles), with the conditions of (3) being 4 hours each for a total of 12 hours.
  • the cured product after the test was visually observed, and the color tone b 1 and haze value H of the cured product after the accelerated weather resistance test were measured.
  • the color tone of the cured product was evaluated by b 1 -b 0 . (1) Temperature 63 ° C, humidity 70% (2) Temperature 70 ° C, humidity 90% (3) Temperature 30 ° C, humidity 98% (with shower for 10 seconds before and after (3))
  • the coating on the resulting laminate, the haze value before abrasion test was measured H 1.
  • a surface of the coating film on the laminate was coated with steel wool # 0000 with a weight of 200 gf (per 4 cm 2 area) using a Gakushin Abrasion Tester (manufactured by Toyo Seiki).
  • the haze value H 2 after placing and reciprocating 15 times was measured. When the haze value H 2 was 30 or less, the scratch resistance was considered excellent.
  • the haze value was measured according to JIS K7105 using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory Co., Ltd.).
  • T-33 polyol represented by the following formula (10) (trade name “Dynesorb T-33” manufactured by Daiwa Kasei Co., Ltd.)
  • T-35 polyol represented by the following formula (11) (trade name “Dynesorb T-35” manufactured by Daiwa Kasei Co., Ltd.)
  • (Polyfunctional acrylate) V-300 A mixture containing 40 to 45% by weight of pentaerythritol triacrylate and 35 to 40% by weight of pentaerythritol tetraacrylate as other compounds (catalog value) (“Biscoat (registered trademark) 300 manufactured by Osaka Organic Chemical Co., Ltd.) ”)
  • UV absorber TINUVIN479: hydroxyphenyltriazine (HPT) ultraviolet absorber (manufactured by BASF)
  • Example 1 In a flask, 56.9 g of urethane acrylate polymer “U-1” (solid content: 50% by weight), 1.4 g of Irg184 as a polymerization initiator, and Polyflow No. 1 as a leveling agent. 0.1 g of 75, 1.6 g of MEK, and 40.0 g of PGM were added and stirred at 25 ° C. for 1 hour to obtain a curable composition. Transparency was evaluated using the obtained curable composition. The obtained results are shown in Table 1.
  • Examples 2 to 5 and Comparative Examples 1 to 7 The same procedure as in Example 1 was performed except that the composition of the curable composition was changed as shown in Table-1. The results obtained for each evaluation item are shown in Table 1. In Examples 2 and 3, U-2 was used, in Examples 4 and 5, U-3 was used, and in Comparative Example 1, U-4 was used instead of U-1.
  • Comparative Examples 2 and 3 in which T-33, which is a dihydroxy compound, was added to the curable composition, the solution was cloudy, the solution appearance was unacceptable, and a good coating film could not be obtained.
  • Comparative Examples 4 and 5 to which T-35 was added had insufficient weather resistance.
  • Comparative Example 6 to which Tinuvin 479 was added the b 1 -b 0 value in the metal weather test (28 cycle weather resistance) increased and the weather resistance decreased. Comparative Example 7 was poor in coating film appearance and weather resistance.
  • a cured product and a laminate obtained by using the urethane (meth) acrylate polymer or the curable composition of the present invention can be suitably used as a coating substitute film.
  • the present invention can be effectively applied to interior and exterior building materials and various members such as automobiles, home appliances, and information electronic materials.
  • the cured film which is embodiment of this invention can be used suitably as a decorating film which uses this as a topcoat layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

La présente invention aborde le problème consistant à fournir : un polymère de (méth)acrylate d'uréthanne qui permet de réaliser un film de revêtement qui empêche une exsudation de l'absorbant des ultraviolets, tout en présentant une excellente résistance aux intempéries, une excellente résistance à la rayure et une excellente transparence ; et une composition durcissable qui contient ce polymère de (méth)acrylate d'uréthanne. La présente invention aborde aussi le problème consistant à fournir un stratifié et un film décoratif, dont chacun présente une couche qui est formée d'un produit durci en le polymère de (méth)acrylate d'uréthanne décrit ci-dessus ou une composition durcissable contenant sur sa surface le polymère de (méth)acrylate d'uréthanne décrit ci-dessus. Ces problèmes sont résolus par un polymère de (méth)acrylate d'uréthanne qui a la structure chimique représentée par la formule (1). (Dans la formule, A représente une simple liaison ou un groupe méthylène, un groupe alkylène, un groupe –O-, un groupe –NH-, un groupe –S-, un groupe –SO- ou un groupe -SO2-, dont chacun peut avoir un substituant ; chacun de R1, R2, R3 et R4 représente d'une manière indépendante un atome d'hydrogène, un groupe alkyle, un groupe alcoxy, un groupe aryle ou un atome d'halogène ; et chacun de R5 et R6 représente d'une manière indépendante un groupe alkylène, un groupe alcoxylène ou un groupe arylène.)
PCT/JP2018/010385 2017-03-17 2018-03-16 Polymère de (méth)acrylate d'uréthanne WO2018169031A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201880018434.0A CN110446736B (zh) 2017-03-17 2018-03-16 聚氨酯（甲基）丙烯酸酯聚合物
JP2019506283A JPWO2018169031A1 (ja) 2017-03-17 2018-03-16 ウレタン（メタ）アクリレート重合体
KR1020197027883A KR102275295B1 (ko) 2017-03-17 2018-03-16 우레탄(메트)아크릴레이트 중합체
JP2022108317A JP2022133387A (ja) 2017-03-17 2022-07-05 ウレタン（メタ）アクリレート重合体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017052242 2017-03-17
JP2017-052242 2017-03-17

Publications (1)

Publication Number Publication Date
WO2018169031A1 true WO2018169031A1 (fr) 2018-09-20

Family

ID=63522358

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/010385 WO2018169031A1 (fr) 2017-03-17 2018-03-16 Polymère de (méth)acrylate d'uréthanne

Country Status (5)

Country Link
JP (2) JPWO2018169031A1 (fr)
KR (1) KR102275295B1 (fr)
CN (1) CN110446736B (fr)
TW (1) TWI750350B (fr)
WO (1) WO2018169031A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102306431B1 (ko) * 2020-01-13 2021-09-30 중앙대학교 산학협력단 전사 몰드용 수지 조성물 및 이를 포함하는 전사 몰드를 이용한 전사 방법
TWI811576B (zh) * 2020-10-26 2023-08-11 南亞塑膠工業股份有限公司 水性聚氨酯樹脂的製備方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010265440A (ja) * 2009-04-15 2010-11-25 Emulsion Technology Co Ltd 紫外線硬化型粘着剤組成物
JP2011207152A (ja) * 2010-03-30 2011-10-20 Nikon-Essilor Co Ltd 光学レンズおよびその製造方法
WO2012026151A1 (fr) * 2010-08-27 2012-03-01 東レ株式会社 Pâte photosensible, procédé de formation de motif et procédé de production d'élément d'écran plat
JP2017165819A (ja) * 2016-03-14 2017-09-21 株式会社ビルドランド 木質用コーティング剤
JP2018016782A (ja) * 2016-02-23 2018-02-01 三菱ケミカル株式会社 ウレタン（メタ）アクリレートオリゴマー
JP2018039199A (ja) * 2016-09-08 2018-03-15 東新油脂株式会社 木質用コーティング剤

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2918543B1 (ja) 1998-07-01 1999-07-12 大塚化学株式会社 塗料組成物
US6703139B1 (en) * 1998-07-10 2004-03-09 Otsuka Chemical Co., Ltd. Weather-resistant composition, coating materials and molded articles
JP3059704B2 (ja) 1998-08-11 2000-07-04 大成化工株式会社 耐候性良好な塗料
JP4304737B2 (ja) 1998-10-01 2009-07-29 荒川化学工業株式会社 紫外線遮蔽活性エネルギー線硬化性組成物、硬化型被覆材料及びそれらが被覆された成型体
JP2002012823A (ja) 2000-04-27 2002-01-15 Kansai Paint Co Ltd 水性塗料組成物
JP4033253B2 (ja) * 2001-11-02 2008-01-16 ダイセル・サイテック株式会社 紫外線吸収性官能基含有ウレタン（メタ）アクリレート及びその組成物
TW200642995A (en) * 2005-03-15 2006-12-16 Showa Denko Kk (Meth)acryloyl group-containing aromatic isocyanate compound and production process thereof
WO2009133770A1 (fr) * 2008-04-30 2009-11-05 Dic株式会社 Composition de revêtement durcissable par un rayonnement d'énergie active, produit durci de celle-ci et nouvelle résine durcissable
CH705596A1 (de) * 2011-10-06 2013-04-15 Eternit Schweiz Ag 2-Komponenten-Beschichtung auf Faserzement.
WO2014003095A1 (fr) * 2012-06-29 2014-01-03 株式会社ネオス Copolymère à base de (méth)acrylate, agent antimicrobien, composition de résine conférant des propriétés antimicrobiennes et composition de résine conférant des propriétés antistatiques
JP6314378B2 (ja) * 2013-07-12 2018-04-25 日油株式会社 硬化性樹脂組成物
JP6458339B2 (ja) * 2013-12-05 2019-01-30 三菱ケミカル株式会社 硬化性樹脂組成物、硬化物及び積層体
JP6672793B2 (ja) * 2013-12-17 2020-03-25 日産化学株式会社 膜形成用組成物
JP6798104B2 (ja) * 2014-12-25 2020-12-09 三菱ケミカル株式会社 ウレタン（メタ）アクリレートの製造方法
CN105733434B (zh) * 2014-12-26 2019-09-24 中国涂料株式会社 光固化性树脂组合物、及固化膜、带膜基材及其制造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010265440A (ja) * 2009-04-15 2010-11-25 Emulsion Technology Co Ltd 紫外線硬化型粘着剤組成物
JP2011207152A (ja) * 2010-03-30 2011-10-20 Nikon-Essilor Co Ltd 光学レンズおよびその製造方法
WO2012026151A1 (fr) * 2010-08-27 2012-03-01 東レ株式会社 Pâte photosensible, procédé de formation de motif et procédé de production d'élément d'écran plat
JP2018016782A (ja) * 2016-02-23 2018-02-01 三菱ケミカル株式会社 ウレタン（メタ）アクリレートオリゴマー
JP2017165819A (ja) * 2016-03-14 2017-09-21 株式会社ビルドランド 木質用コーティング剤
JP2018039199A (ja) * 2016-09-08 2018-03-15 東新油脂株式会社 木質用コーティング剤

Also Published As

Publication number Publication date
CN110446736B (zh) 2021-09-28
TW201840621A (zh) 2018-11-16
KR20190115477A (ko) 2019-10-11
TWI750350B (zh) 2021-12-21
JP2022133387A (ja) 2022-09-13
KR102275295B1 (ko) 2021-07-12
JPWO2018169031A1 (ja) 2020-01-16
CN110446736A (zh) 2019-11-12

Similar Documents

Publication Publication Date Title
JP5445215B2 (ja) 活性エネルギー線硬化性樹脂組成物、硬化膜及び積層体
KR101887722B1 (ko) 장식 시트 및 이것을 사용한 장식 수지 성형품
JP6458339B2 (ja) 硬化性樹脂組成物、硬化物及び積層体
JP5664970B2 (ja) 活性エネルギー線硬化型樹脂組成物
JP6123428B2 (ja) 活性エネルギー線硬化性樹脂組成物、該組成物による硬化膜、及び該硬化膜を有する積層体
JP2022133387A (ja) ウレタン（メタ）アクリレート重合体
JP5853859B2 (ja) プラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物
JP6520301B2 (ja) 硬化性組成物
EP2216359A1 (fr) Procédé de formation d'un film de revêtement
JP2010260905A (ja) 光硬化性組成物
JP6451627B2 (ja) 活性エネルギー線硬化性樹脂組成物及び自動車ヘッドランプレンズ
JP6903941B2 (ja) ウレタン（メタ）アクリレートオリゴマー
JP5255962B2 (ja) 活性エネルギー線硬化性被膜形成組成物
JP2014065903A (ja) 活性エネルギー線硬化性樹脂組成物及びコーティング剤
JP2021102285A (ja) ３次元成型品加飾用積層フィルム、その製造方法及び３次元加飾方法
JP2014231591A (ja) ウレタン（メタ）アクリレートオリゴマー、硬化性樹脂組成物、硬化物及び積層体
JP2002285062A (ja) 活性エネルギー線硬化型印刷用インキ組成物
JP7060071B2 (ja) ウレタン（メタ）アクリレートオリゴマー
JP2017186404A (ja) 硬化性組成物
JP6816790B2 (ja) ウレタン（メタ）アクリレートオリゴマー
JP6705165B2 (ja) ウレタン（メタ）アクリレートオリゴマー
WO2019182155A1 (fr) Composition durcissable, produit durci, procédé de production d'un produit durci, et procédé de réparation d'un endommagement d'un produit durci
JP6340756B2 (ja) 硬化性樹脂組成物及び硬化膜
WO2019117030A1 (fr) Composition de résine durcissable par rayonnement d'énergie active et agent de revêtement
JP7434708B2 (ja) 活性エネルギー線硬化性樹脂組成物及びコーティング剤

Legal Events

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

Ref document number: 18766637

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019506283

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20197027883

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 18766637

Country of ref document: EP

Kind code of ref document: A1