WO2016093005A1 - (méth)acrylate d'uréthane, composition de (méth)acrylate d'uréthane durcissable par un rayonnement d'énergie active et article durci associé - Google Patents

(méth)acrylate d'uréthane, composition de (méth)acrylate d'uréthane durcissable par un rayonnement d'énergie active et article durci associé Download PDF

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WO2016093005A1
WO2016093005A1 PCT/JP2015/081595 JP2015081595W WO2016093005A1 WO 2016093005 A1 WO2016093005 A1 WO 2016093005A1 JP 2015081595 W JP2015081595 W JP 2015081595W WO 2016093005 A1 WO2016093005 A1 WO 2016093005A1
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meth
acrylate
urethane
lactone
isocyanate
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PCT/JP2015/081595
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English (en)
Japanese (ja)
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長川伊知郎
渡部淳
畑中慎太郎
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ダイセル・オルネクス株式会社
株式会社ダイセル
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    • 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
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/12—Esters of phenols or saturated alcohols
    • C08F22/22—Esters containing nitrogen
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen

Definitions

  • the present invention relates to urethane (meth) acrylate (active energy ray-curable urethane (meth) acrylate) mainly useful for paints, coating applications, and the like, and a composition containing this as a curing component (active energy ray-curable urethane (meta)). ) Acrylate composition) and its cured product.
  • Such an active energy ray-curable coating material contains a resin curable with active energy rays and a curable monomer, and the monomer simultaneously functions as a solvent.
  • resins and monomers for example, oligomers having a (meth) acryloyl group at the molecular ends such as urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, acrylic monomers, and the like are used. ing.
  • urethane (meth) acrylate resin has a good balance of physical properties
  • coating compositions using the resin include, for example, decorative paper coating, paper luster (OPV), woodworking paint, plastics hard coating, Widely used in inks.
  • the formed coating film is required to have performance such as hardness, curl resistance, flexibility, and adhesion, and the above-mentioned active energy ray-curable material.
  • performance such as hardness, curl resistance, flexibility, and adhesion, and the above-mentioned active energy ray-curable material.
  • various performance improvements have been studied.
  • urethane (meth) acrylate resin for example, a hydroxyl group-containing polyfunctional (meth) acrylate compound having one or more polymerizable unsaturated bonds and an isocyanate group having an isocyanate group and an isocyanurate ring structure in one molecule
  • An unsaturated urethane compound containing 6 or more polymerizable unsaturated groups in one molecule obtained by a reaction between an isocyanate group-containing urethane compound comprising a compound and a hydroxyl group-containing compound having a hydroxyl group and an isocyanurate ring structure in one molecule (See Patent Document 1); an isocyanate group-containing unsaturated urethane compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound having one or more polymerizable unsaturated bonds in one molecule and an isocyanurate compound having an isocyanate group; Hydro with two or more hydroxyl groups in one molecule An unsaturated urethane compound containing
  • a coating agent containing an unsaturated urethane compound or urethane (meth) acrylate disclosed in Patent Documents 1 to 3 is applied to an object to be coated (for example, a substrate such as a film) and cured by irradiation with ultraviolet rays, whereby a cured coating is obtained.
  • a film can be formed.
  • the surface of the cured coating film (hard coat layer) thus obtained is hard, but on the other hand, it has a problem of causing curling of the coated object after irradiation with ultraviolet rays.
  • cur resistance a material capable of forming a cured coating film having a good balance between the surface hardness and the property of hardly causing curling of an object to be coated
  • an object of the present invention is to provide a material (urethane (meta) which can form a coating film (cured coating film) having a good balance between high surface hardness (for example, abrasion resistance, scratch resistance) and curl resistance. ) Acrylate), and an active energy ray-curable resin composition (active energy ray-curable urethane (meth) acrylate composition) containing the material.
  • a material urethane (meta) which can form a coating film (cured coating film) having a good balance between high surface hardness (for example, abrasion resistance, scratch resistance) and curl resistance.
  • an active energy ray-curable resin composition active energy ray-curable urethane (meth) acrylate composition
  • the inventors of the present invention have a high surface hardness according to a urethane (meth) acrylate using a specific compound as a raw material and an active energy ray-curable urethane (meth) acrylate composition containing the same.
  • the present invention has been completed by finding that a coating film (cured coating film) having a good balance between the two properties of curling and curling can be formed.
  • a lactone-modified hydroxyl group-containing poly (meth) acrylate (A) obtained by adding 1 to 6 moles of lactone to 1 mole of hydroxyalkyl poly (meth) acrylate, and one or more isocyanate groups per molecule Urethane (meth) acrylate obtained by reacting with an isocyanate compound (B).
  • a lactone-modified hydroxyl group-containing poly (meth) acrylate (A) obtained by adding 1 to 6 moles of lactone to 1 mole of hydroxyalkyl poly (meth) acrylate, and two or more isocyanate groups per molecule
  • Urethane (meth) acrylate obtained by reacting an isocyanate compound (B1) with a polyol (C) having two or more hydroxyl groups per molecule.
  • An active energy ray-curable urethane (meth) acrylate composition comprising the urethane (meth) acrylate according to any one of [1] to [3].
  • Urethane (meth) acrylate obtained by reacting an isocyanate compound (B1) with a polyol (C) having two or more hydroxyl groups per molecule.
  • B1> The urethane (meth) acrylate according to ⁇ 1> or ⁇ 2>, wherein the hydroxyalkyl poly (meth) acrylate is a compound represented by the following formula (1).
  • R 1 in the compound represented by the formula (1) is a (p + 1) -valent linear or branched aliphatic hydrocarbon group, and p is an integer of 2 to 10, preferably 2 to The urethane (meth) acrylate according to ⁇ 3>, which is an integer of 6, more preferably an integer of 2 to 4.
  • Hydroxyalkyl poly (meth) acrylate selected from the group consisting of pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, and dipentaerythritol penta (meth) acrylate
  • the urethane (meth) acrylate according to any one of ⁇ 1> to ⁇ 4> which is at least one selected from the group consisting of: ⁇ 6>
  • the lactone is at least one selected from the group consisting of ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and lower alkyl substituents of these lactones ⁇
  • urethane (meth) acrylate according to any one of ⁇ 1> to ⁇ 8>, wherein the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) is represented by the following formula (2).
  • R 3 in formula (2) is an alkylene group having 2 to 6 carbon atoms.
  • R 3 in formula (2) is a pentamethylene group.
  • the number of isocyanate groups in the molecule of the isocyanate compound (B) is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4.
  • Isocyanate compound (B) is an aromatic isocyanate compound, an aliphatic isocyanate compound, a cycloaliphatic isocyanate compound, an alicyclic isocyanate compound, a mixture of these isocyanate compounds, an adduct of the above isocyanate compound, or the above
  • Isocyanate compound (B) is 2-acryloyloxyethyl isocyanate (AOI), 2-methacryloyloxyethyl isocyanate (MOI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H12MDI).
  • AOI 2-acryloyloxyethyl isocyanate
  • MOI 2-methacryloyloxyethyl isocyanate
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • H12MDI hydrogenated diphenylmethane diisocyanate
  • Polyphenylmethane isocyanate compound (crude MDI), modified diphenylmethane diisocyanate (modified MDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H-XDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NDI), and these One or at least one selected from two or more of the group consisting of trimeric compounds ⁇ 1> to urethane (meth) acrylate according to any one of ⁇ 13> of the isocyanate compound.
  • ⁇ 15> The urethane (meth) acrylate according to any one of ⁇ 2> to ⁇ 14>, wherein the polyol (C) is a diol or a polyol having three or more hydroxy groups in the molecule.
  • ⁇ 17> An active energy ray-curable urethane (meth) acrylate composition comprising the urethane (meth) acrylate according to any one of ⁇ 1> to ⁇ 16>.
  • the content (blending amount) of urethane (meth) acrylate is 30% by weight or more (for example, 30 to 99 with respect to the total amount (100% by weight) of the active energy ray-curable urethane (meth) acrylate composition)
  • the active energy ray-curable urethane (meth) acrylate composition according to ⁇ 17> preferably 50 to 98% by weight, more preferably 55 to 90% by weight.
  • ⁇ 20> The active energy ray-curable urethane (meth) acrylate composition according to any one of ⁇ 17> to ⁇ 19>, further comprising a photopolymerization initiator.
  • ⁇ 21> A cured product obtained by curing the active energy ray-curable urethane (meth) acrylate composition according to any one of ⁇ 17> to ⁇ 20>.
  • the cured product formed by curing the active energy ray-curable urethane (meth) acrylate composition containing the urethane (meth) acrylate as an essential component has a high surface. It has a good balance of both hardness (for example, wear resistance, scratch resistance) and curl resistance.
  • the active energy ray-curable urethane (meth) acrylate composition of the present invention is a coating agent (coating application), a paint (coating application), an adhesive (adhesive agent) that forms a cured coating film on the surface of an article. It can be preferably used for applications).
  • 2 is a chart of 1 H-NMR spectrum of a product obtained in Synthesis Example 1.
  • 2 is a chart of 1 H-NMR spectrum of a product obtained in Synthesis Example 2.
  • 1 is a chart of 1 H-NMR spectrum of urethane acrylate (UA1) obtained in Example 1.
  • the chart of IR spectrum of urethane acrylate (UA1) obtained in Example 1 is shown.
  • the GPC elution curve of the urethane acrylate (UA1) obtained in Example 1 is shown.
  • 2 is a chart of 1 H-NMR spectrum of urethane acrylate (UA2) obtained in Example 2.
  • the chart of IR spectrum of urethane acrylate (UA2) obtained in Example 2 is shown.
  • the GPC elution curve of the urethane acrylate (UA2) obtained in Example 2 is shown.
  • the urethane (meth) acrylate of the present invention is a lactone modified with 1 to 6 moles of lactone added to 1 mole of hydroxyalkyl poly (meth) acrylate (that is, 1 mole of hydroxyl group of hydroxyalkyl poly (meth) acrylate).
  • Hydroxyl group-containing poly (meth) acrylate (A) (sometimes referred to as “lactone-modified hydroxyl group-containing poly (meth) acrylate (A)”, “component (A)”, “A”)) and one or more per molecule
  • urethane (meth) acrylates obtained by reacting at least a compound having an isocyanate group (sometimes referred to as “isocyanate compound (B)”, “component (B)”, or “B”).
  • Urethane (meth) acrylate of the present invention [1] Urethane (meth) acrylate obtained by reacting lactone-modified hydroxyl group-containing poly (meth) acrylate (A) with isocyanate compound (B), and [2] Lactone-modified hydroxyl group-containing poly (meth) acrylate (A ),
  • An isocyanate compound having two or more isocyanate groups per molecule sometimes referred to as “isocyanate compound (B1)", “component (B1)”, “B1"
  • Urethane (meth) acrylate obtained by reacting a compound having a hydroxyl group sometimes referred to as “polyol (C)”, “component (C)”, “C”
  • the urethane (meth) acrylate of the present invention is not limited to these embodiments as long as it is obtained by reacting at least the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) and the isocyanate compound (B). .
  • (meth) acrylate means acrylate and / or methacrylate (any one or both of acrylate and methacrylate), and the same applies to “(meth) acryloyl” and the like.
  • the average number of functional groups of the urethane (meth) acrylate of the present invention is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15.
  • the surface hardness (scratch resistance, abrasion resistance, etc.) of the cured product (cured coating film) tends to be higher.
  • the average number of functional groups is 20 or less, the curled resistance of the cured product (cured coating film) tends to be further improved.
  • the “average functional group number” of the urethane (meth) acrylate of the present invention is the average number of (meth) acryloyl groups possessed by one molecule of the urethane (meth) acrylate of the present invention.
  • the urethane (meth) acrylate obtained by reacting at a molar ratio of 1: 1 has 3 average functional groups.
  • the structure is schematically shown as follows.
  • a polyol (C) which is a diol having two hydroxyl groups per molecule
  • an isocyanate compound (B1) which is a diisocyanate having two isocyanate groups per molecule, one hydroxyl group and three molecules per molecule
  • the average number of functional groups of urethane (meth) acrylate obtained by reacting lactone-modified hydroxyl group-containing poly (meth) acrylate (A) having a (meth) acryloyl group in a molar ratio of 1: 2: 2 is 6.
  • the structure is schematically shown as follows.
  • polyol (C) which is a diol having two hydroxyl groups per molecule
  • isocyanate compound (B1) which is a triisocyanate having three isocyanate groups per molecule, one hydroxyl group and 3 per molecule.
  • the average number of functional groups of urethane (meth) acrylate obtained by reacting lactone-modified hydroxyl group-containing poly (meth) acrylate (A) having one (meth) acryloyl group at a molar ratio of 1: 2: 4 is 12.
  • the structure is schematically shown as follows.
  • the urethane (meth) acrylate of the present invention may be a mixture of two or more of the same or different average functional group numbers.
  • the average number of functional groups of the mixture can be determined by a weighted average. For example, 0.3 mol of urethane (meth) acrylate having 3 average functional groups, 0.2 mol of urethane (meth) acrylate having 6 average functional groups, and 0.5 mol of urethane (meth) acrylate having 12 average functional groups
  • the weight average molecular weight of the urethane (meth) acrylate of the present invention is not particularly limited, but is preferably 500 to 30,000, more preferably 800 to 10,000. By setting the weight average molecular weight to 500 or more, the surface hardness and mechanical strength of the cured product (cured coating film) tend to be further improved. On the other hand, by setting the weight average molecular weight to 30000 or less, the viscosity of the active energy ray-curable urethane (meth) acrylate composition does not become too high, and the handleability in coating work and the like is further improved, and an excellent cured coating film. Tends to be obtained. In addition, the weight average molecular weight of the urethane (meth) acrylate of this invention is computed from the molecular weight of standard polystyrene conversion measured by gel permeation chromatography.
  • lactone-modified hydroxyl group-containing poly (meth) acrylate (A) The lactone-modified hydroxyl group-containing poly (meth) acrylate (A), which is a raw material for the urethane (meth) acrylate of the present invention, will be described.
  • the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) is a compound in which 1 to 6 moles of lactone is added to 1 mol of hydroxyalkyl poly (meth) acrylate, and 1 mol of hydroxyalkyl poly (meth) acrylate is added to 1 mol of hydroxyalkyl poly (meth) acrylate.
  • the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) has a specific amount of a structure modified with a lactone (that is, a structure in which the lactone is ring-opened), and one hydroxyl group per molecule and 1 It has two or more (meth) acryloyl groups per molecule.
  • the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) can be used alone or in combination of two or more. .
  • the hydroxyalkyl poly (meth) acrylate which is a raw material of the lactone-modified hydroxyl group-containing poly (meth) acrylate (A), has one hydroxyl group per molecule, and two or more (meth) acryloyl groups per molecule. It is a compound that has.
  • the hydroxyalkyl poly (meth) acrylate does not have a structure modified with a lactone.
  • or usual compound can be used, although it does not specifically limit, For example, the compound represented by following formula (1) can be used.
  • R 1 represents a (p + 1) -valent hydrocarbon group.
  • (p + 1) is an integer of 3 or more.
  • the hydrocarbon group include a trivalent or higher linear, branched or cyclic aliphatic hydrocarbon group; a trivalent or higher aromatic hydrocarbon group; a linear aliphatic hydrocarbon group; a branched fatty acid.
  • Examples of the trivalent straight chain, branched chain, or cyclic aliphatic hydrocarbon group include, for example, alkane-triyl group [for example, methane-triyl group, ethane-triyl group ((meth) acryloyloxy group and hydroxyl bonding position) The same applies to the groups that do not specify the bonding position as exemplified below), propane-triyl group, 1,1,1-trimethylpropane-triyl group, etc.], cycloalkane-triyl group [for example, cyclohexane-triyl group , Methylcyclohexane-triyl group, dimethylcyclohexane-triyl group, etc.].
  • alkane-triyl group for example, methane-triyl group, ethane-triyl group ((meth) acryloyloxy group and hydroxyl bonding position)
  • propane-triyl group 1,1,1-trimethylprop
  • Examples of the trivalent aromatic hydrocarbon group include groups formed by removing three hydrogen atoms from an aromatic compound such as benzene, naphthalene, and fluorene on the structural formula.
  • Examples of the tetravalent straight chain, branched chain, or cyclic aliphatic hydrocarbon group include an alkane-tetrayl group [eg, methane-tetrayl group, ethane-tetrayl group, propane-tetrayl group, butane-tetrayl group, 2 , 2-dimethylpropane-tetrayl group, etc.], cycloalkane-tetrayl group [for example, cyclohexane-tetrayl group, methylcyclohexane-tetrayl group, dimethylcyclohexane-tetrayl group] and the like.
  • Examples of the tetravalent aromatic hydrocarbon group include a group formed by removing four hydrogen atoms from an
  • R 1 a (p + 1) -valent linear or branched aliphatic hydrocarbon group is preferable because it is excellent in balance between the surface hardness of the cured coating film and the curl resistance.
  • R 2 represents a hydrogen atom or a methyl group. Each R 2 may be the same or different.
  • P represents an integer of 2 or more (for example, an integer of 2 to 10), preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.
  • examples of the hydroxyalkyl poly (meth) acrylate include pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, and dipentaerythritol penta (meth).
  • An acrylate etc. are mentioned.
  • a compound having 3 or more (meth) acryloyl groups (total) per molecule is preferable, and pentaerythritol tri (meth) is more preferable because it is excellent in balance between the surface hardness and curl resistance of the cured coating film.
  • Acrylate a compound having 3 or more (meth) acryloyl groups (total) per molecule is preferable, and pentaerythritol tri (meth) is more preferable because it is excellent in balance between the surface hardness and curl resistance of the cured coating film.
  • the hydroxyalkyl poly (meth) acrylate can be produced by a known or conventional method, or is a commercially available product (for example, trade names “PETRA”, “PETIA” (above, manufactured by Daicel Ornex Corporation)). Trade name “Aronix M305” (manufactured by Toagosei Co., Ltd.) and the like can also be obtained.
  • the lactone that is a raw material of the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) can be a known or commonly used lactone, and is not particularly limited.
  • ⁇ -caprolactone is preferable because it is excellent in the balance between the surface hardness of the cured coating film and the curl resistance.
  • lactone can also be used individually by 1 type and can also be used in combination of 2 or more type.
  • the lactone can be produced by a known or conventional method, or a commercially available product can be obtained.
  • the reaction between the hydroxyalkyl poly (meth) acrylate and the lactone is a reaction in which a lactone is added to the hydroxyl group of the hydroxyalkyl poly (meth) acrylate (ring-opening addition reaction or ring-opening addition polymerization).
  • the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) is a compound having a structure in which a lactone is added (ring-opening addition or ring-opening addition polymerization) starting from a hydroxyl group in the hydroxyalkyl poly (meth) acrylate.
  • the amount of lactone to be added to the hydroxyalkyl poly (meth) acrylate is 1 as described above with respect to 1 mol of hydroxyalkyl poly (meth) acrylate (that is, 1 mol of hydroxyl group of hydroxyalkyl poly (meth) acrylate). -6 mole times, preferably 1-5 mole times.
  • reaction between hydroxyalkyl poly (meth) acrylate and lactone can be carried out by a known or conventional method and is not particularly limited, but can usually be carried out by heating both.
  • other components such as a cocatalyst and a polymerization inhibitor can be used as necessary.
  • the said reaction may be advanced in one step, and may be made to advance sequentially in two or more steps.
  • the above reaction can be allowed to proceed in an organic solvent or can be allowed to proceed in the absence of an organic solvent. It does not specifically limit as said organic solvent, For example, what was illustrated as a volatile organic solvent in reaction of the below-mentioned component (A) and component (B) can be used.
  • hydroxyalkyl poly (meth) acrylate and lactone can be charged and reacted together in a reaction vessel, or hydroxyalkyl poly (meth) acrylate and lactone can be reacted. Either one can be charged in a reaction vessel and the other can be added (for example, sequentially added) to cause the reaction.
  • reaction temperature in the above reaction is not particularly limited, and can be appropriately selected from the range of 80 to 250 ° C. (for example, 100 to 200 ° C.). Further, the time for carrying out the above reaction (reaction time) is not particularly limited, and can be appropriately selected from the range of, for example, 0.2 to 20 hours (for example, 1 to 8 hours).
  • the above reaction can be carried out under normal pressure, under pressure or under reduced pressure.
  • the atmosphere in which the above reaction is performed is not particularly limited, and the reaction can be performed in any atmosphere such as an inert gas (for example, nitrogen, argon, or the like) or air.
  • the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) is generated by the above reaction.
  • the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) is, for example, a known or commonly used separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. Can be separated and purified.
  • the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) can be used as it is without being separated and purified.
  • the number of hydroxyl groups per molecule and the number of (meth) acryloyl groups in the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) obtained by the above reaction are usually the same as the raw material hydroxyalkyl poly (meth) acrylate. It is the same as the number of hydroxyl groups per molecule and the number of (meth) acryloyl groups.
  • the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) is represented by the following formula (2), for example.
  • R 1 , R 2 , and p are the same as those in formula (1).
  • R 3 in the formula (2) represents a linear or branched alkylene group having 2 or more carbon atoms.
  • the alkylene group include alkylene groups having 2 to 6 carbon atoms such as ethylene group, propylene group, trimethylene group, tetramethylene group, isobutylene group, pentamethylene group, and hexamethylene group. Of these, a pentamethylene group is preferable.
  • q is an integer greater than or equal to 2
  • each R ⁇ 3 > may be the same and may differ.
  • Q in formula (2) is the number of repetitions of the structure in parentheses with q, and represents an integer of 1-6.
  • q is preferably an integer of 1 to 5.
  • the urethane (meth) acrylate of the present invention is presumably due to the above-mentioned characteristic structure of the lactone-modified hydroxyl group-containing poly (meth) acrylate (A).
  • R in the formula (2) Compared to the case of using a compound having a structure modified with lactone between 1 and (meth) acryloyloxy group, the surface hardness is higher and the curl resistance is more excellent. It is possible to form a cured coating film that is well balanced.
  • the isocyanate compound (B) that is a raw material of the urethane (meth) acrylate of the present invention will be described.
  • the isocyanate compound (B) is a compound having one or more isocyanate groups per molecule.
  • the isocyanate compound (B) can also be used individually by 1 type as a raw material of the urethane (meth) acrylate of this invention, and can also be used in combination of 2 or more type.
  • the number of isocyanate groups in the molecule of the isocyanate compound (B) is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. In the present specification, as described above, among the isocyanate compounds (B), those having two or more isocyanate groups per molecule may be referred to as “isocyanate compounds (B1)”.
  • isocyanate compound (B) an aromatic isocyanate compound, an aliphatic isocyanate compound, a cycloaliphatic isocyanate compound, an alicyclic isocyanate compound, a mixture of these isocyanate compounds, an adduct of the above isocyanate compound, and the above isocyanate compound
  • Known isocyanate compounds such as modified products of the above and polymers of the above isocyanate compounds can be used.
  • isocyanate compound (B) for example, 2-acryloyloxyethyl isocyanate (AOI), 2-methacryloyloxyethyl isocyanate (MOI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), water Hydrogenated diphenylmethane diisocyanate (H12MDI), polyphenylmethane isocyanate compound (crude MDI), modified diphenylmethane diisocyanate (modified MDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H-XDI), hexamethylene diisocyanate (HDI) ), Trimethylhexamethylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate Isocyanate compounds such as (NDI); 1, two or more of the trimer compounds of these is
  • the isocyanate compound (B) can be produced by a known or conventional method, or a commercially available product can be obtained.
  • Commercially available products include, for example, the product name “VESTANAT IPDI” (isophorone diisocyanate, manufactured by Evonik), the product name “2-acryloyloxyethyl isocyanate” (manufactured by Showa Denko KK), and the product name “Takenate D-170N” ( 1,6-hexamethylene diisocyanate trimer, manufactured by Mitsui Chemicals, Inc., trade name “Sumijour N3300” (trimer of 1,6-hexamethylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.), etc. Can be mentioned.
  • Polyol (C) The polyol (C) that is a raw material of the urethane (meth) acrylate of the present invention will be described.
  • the polyol (C) is a compound having two or more hydroxyl groups per molecule.
  • a polyol (C) can also be used individually by 1 type as a raw material of the urethane (meth) acrylate of this invention, and can also be used in combination of 2 or more type.
  • polyol (C) known or commonly used compounds having two or more hydroxyl groups per molecule can be used, and are not particularly limited.
  • Polyol (C) can be produced by a known or conventional method, or a commercially available product can be obtained.
  • a commercial item a brand name "Nipporan” series (Nippon Polyurethane Industry Co., Ltd. product) etc. are mentioned, for example.
  • the urethane (meth) acrylate of the present invention is obtained by reacting at least the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) with the isocyanate compound (B).
  • the urethane (meth) acrylate of the present invention is obtained, for example, by reacting the urethane (meth) acrylate (lactone-modified hydroxyl group-containing poly (meth) acrylate (A) and the isocyanate compound (B) of [1] above.
  • the urethane (meth) acrylate can be produced by reacting the component (A) and the component (B).
  • the method for reacting the above component (A) and component (B) is not particularly limited, and examples thereof include the following methods. [Method 1a] Method of mixing component (A) and component (B) and reacting them together [Method 2a] Method of sequentially adding component (B) to component (A) and reacting them [Method 3a] Method in which component (A) is sequentially added to component (B) and these are reacted
  • the “sequential addition” means continuous addition (a mode of adding over a certain period of time) or intermittent addition (a mode of split addition in multiple times).
  • the aspect of sequential addition the aspect of dripping etc. are mentioned, for example. The same applies to [Method 2b-2] described later.
  • [Method 1a] to [Method 3a] are preferably [Method 2a] and [Method 3a] from the viewpoint of controlling the heat of reaction.
  • the reaction between the component (A) and the component (B) described above is preferably allowed to proceed in the presence of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, 4-methoxyphenol for the purpose of preventing polymerization.
  • a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, 4-methoxyphenol for the purpose of preventing polymerization.
  • the addition amount (use amount) of the polymerization inhibitor is not particularly limited, but is preferably 1 to 10,000 ppm, more preferably 100 to 1000 ppm, and still more preferably, based on the weight of the urethane (meth) acrylate of the present invention to be produced. 400 to 500 ppm. If the addition amount of the polymerization inhibitor is less than 1 ppm, a sufficient polymerization inhibition effect may not be obtained. On the other hand, when the addition amount of the polymerization inhibitor exceeds 10,000 ppm, there is
  • the reaction between the component (A) and the component (B) is preferably performed in a gas atmosphere containing molecular oxygen.
  • the oxygen concentration is appropriately selected in consideration of safety.
  • a catalyst in order to obtain a sufficient reaction rate.
  • the catalyst include dibutyltin dilaurate, tin octylate, tin chloride and the like. Of these, dibutyltin dilaurate and the like are preferable from the viewpoint of reaction rate.
  • the addition amount (use amount) of the catalyst is not particularly limited, but is usually preferably 1 to 3000 ppm, more preferably 50 to 1000 ppm, based on weight. When the addition amount of the catalyst is less than 1 ppm, a sufficient reaction rate may not be obtained. On the other hand, if it exceeds 3000 ppm, the physical properties of the urethane (meth) acrylate of the present invention may be adversely affected.
  • the reaction of the above component (A) and component (B) can be allowed to proceed in the presence of a known volatile organic solvent.
  • the volatile organic solvent is not particularly limited, and examples thereof include ethyl acetate, butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl acetate, xylene, toluene and the like. It is done. Of these, ethyl acetate and butyl acetate are preferred from the viewpoints of boiling point and economy. In the above reaction, a volatile organic solvent may not be used.
  • a reactive diluent can be used instead of the volatile organic solvent.
  • the below-mentioned (meth) acryloyl group containing monomer etc. can be used.
  • a reactive diluent a composition containing the urethane (meth) acrylate of the present invention and the reactive diluent is obtained as a product.
  • the said reactive diluent is the urethane of this invention (for the purpose of adjustment of the viscosity of the below-mentioned active energy ray hardening-type urethane (meth) acrylate composition, adjustment of the surface hardness of a cured coating film, etc.) as needed. It can also be blended after the (meth) acrylate is formed.
  • 1,6-hexanediol diacrylate for example, product name “HDDA” manufactured by Daicel Ornex Co., Ltd.
  • trimethylolpropane triacrylate for example, the company
  • TMPTA trimethylolpropane triacrylate
  • IRR214-K tricyclodecane dimethanol diacrylate
  • reaction temperature a temperature of 130 ° C. or lower, more preferably 50 to 130 ° C.
  • reaction temperature a temperature of 130 ° C. or lower, more preferably 50 to 130 ° C.
  • reaction temperature exceeds 130 ° C.
  • radical polymerization by heat proceeds to crosslink the double bond portion, and a gelled product may be generated.
  • reaction temperature is less than 50 ° C., a practically sufficient reaction rate may not be obtained.
  • the reaction of the above-mentioned component (A) and component (B) is usually carried out until the isocyanate group concentration (residual isocyanate group concentration) is 0.1% by weight or less.
  • the isocyanate group concentration can be analyzed by, for example, IR (infrared spectroscopy), titration method and the like.
  • the measurement of the isocyanate group concentration by titration is carried out as follows. In addition, a measurement is performed by stirring with a stirrer with a 100 mL glass flask. First, a blank value is measured as follows. To 15 mL of THF, add 15 mL of dibutylamine in THF (0.1 N). Further, after adding 3 drops of bromophenol blue (diluted in 1% by weight of methanol) to give a blue color, titration is performed with an aqueous HCl solution having a normality of 0.1N. The titration amount of the aqueous HCl solution when the color change is observed is defined as Vb (mL).
  • the measured isocyanate group concentration is measured.
  • a sample is weighed with Ws (g), dissolved in 15 mL of THF, and 15 mL of a THF solution (0.1 N) of dibutylamine is added.
  • 3 drops of bromophenol blue (diluted in 1% by weight of methanol) are added to give a blue color, followed by titration with an aqueous HCl solution having a normality of 0.1N.
  • the titration amount of the aqueous HCl solution when the color change is observed is defined as Vs (mL).
  • concentration in a sample is computed with the following formulas.
  • Isocyanate group concentration (% by weight) (Vb ⁇ Vs) ⁇ 1.005 ⁇ 0.42 ⁇ Ws
  • the urethane (meth) acrylate of the present invention has, for example, the urethane (meth) acrylate (lactone-modified hydroxyl group-containing poly (meth) acrylate (A) of [2] and two or more isocyanate groups per molecule.
  • it is a urethane (meth) acrylate obtained by reacting an isocyanate compound (B1) with a compound (C) having two or more hydroxyl groups per molecule, the component (A), the component (B1), and the component It can be produced by reacting (C).
  • the urethane (meth) acrylate of the present invention increases the by-product amount of the following urethane isocyanate prepolymer by repeating the isocyanate compound (B1) and the polyol (C), which is cured. It may cause a decrease in scratch resistance and abrasion resistance of the coating film.
  • quality control since various complex compounds are irregularly produced, quality control may be difficult when the obtained product is used as an active energy ray-curable urethane (meth) acrylate composition or a component thereof. is there.
  • the method for synthesizing the urethane isocyanate prepolymer in [Method 2b] is not particularly limited.
  • the following [Method 2b-1] or [Method 2b-2] is preferably used in order to obtain the desired urethane isocyanate prepolymer with good yield.
  • [Method 2b-1] Method of mixing component (B1) and component (C) and reacting them together
  • [Method 2b-2] Adding component (C) to component (B1) sequentially and reacting them How to make
  • Method 2b-1 A reactor is charged with an isocyanate compound (B1), a polyol (C), and, if necessary, a diluting solvent (for example, ethyl acetate, butyl acetate, etc.).
  • a method in which the reaction (urethanization) between the component (B1) and the component (C) is started or advanced by introducing the catalyst is preferred.
  • the temperature may be increased as necessary after the urethanization catalyst is added.
  • the urethanization reaction proceeds in a non-uniform state of the isocyanate compound (B1) and the polyol (C) at the stage of charging the isocyanate compound (B1), and the resulting urethane isocyanate
  • the molecular weight and viscosity of the prepolymer change, and the reaction may be terminated in the state where the unreacted isocyanate compound (B1) remains in the system.
  • a by-product is generated due to the reaction between the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) to be used later and the remaining isocyanate compound (B1) alone.
  • this method may not be preferred when product uniformity is required.
  • the above method can be adopted.
  • the content of such by-products is preferably less than 15% by weight with respect to the total amount of the product. By making it less than 15% by weight, the balance between the surface hardness of the cured product (cured coating film) and the curl resistance tends to be better.
  • [Method 2b-1] is industrially superior in that the urethane (meth) acrylate of the present invention can be produced in one pot.
  • Method 2b-2 For [Method 2b-2]: Into the reactor, an isocyanate compound (B1), a urethanization catalyst, and, if necessary, a diluting solvent (for example, ethyl acetate, butyl acetate, etc.) are charged and stirred until uniform. Next, while stirring, the temperature is raised as necessary, and the polyol (C) is added successively.
  • a diluting solvent for example, ethyl acetate, butyl acetate, etc.
  • Method 2b-2 is preferable in that the by-product of the following by-product is the least.
  • the urethane isocyanate prepolymer is synthesized by the reaction of the isocyanate compound (B1) and the polyol (C)
  • the isocyanate compound (B1) and the polyol (C) are combined with the isocyanate group concentration in the reaction solution. It is preferable to make the reaction occur until the end point isocyanate group concentration is lower than or equal to the end point isocyanate group concentration.
  • end-point isocyanate group concentration is a theoretical isocyanate group concentration (hereinafter, sometimes referred to as “theoretical end-point isocyanate group concentration”) on the assumption that all of the hydroxyl groups charged into the system are urethanized. This means the higher isocyanate group concentration, which is the higher than the isocyanate group concentration when the isocyanate group concentration in the reaction solution no longer changes.
  • the reaction of urethane isocyanate prepolymer and lactone-modified hydroxyl group-containing poly (meth) acrylate (A) in [Method 2b] is forbidden to polymerize hydroquinone, hydroquinone monomethyl ether, phenothiazine, 4-methoxyphenol, etc. for the purpose of preventing polymerization. It is preferable to proceed in the presence of an agent.
  • the addition amount (use amount) of the polymerization inhibitor is preferably 1 to 10,000 ppm, more preferably 100 to 1000 ppm, and still more preferably 400 to 500 ppm, based on the weight of the urethane (meth) acrylate of the present invention to be produced. .
  • the addition amount of the polymerization initiator is less than 1 ppm, a sufficient polymerization inhibition effect may not be obtained.
  • the addition amount of the polymerization initiator exceeds 10,000 ppm, there is a possibility that various physical properties of the urethane (meth) acrylate of the present invention are adversely affected.
  • the reaction of the urethane isocyanate prepolymer and the component (A) is preferably performed in a gas atmosphere containing molecular oxygen.
  • the oxygen concentration is appropriately selected in consideration of safety.
  • a catalyst in order to obtain a sufficient reaction rate.
  • the catalyst include dibutyltin dilaurate and tin octylate. Of these, dibutyltin dilaurate and the like are preferable from the viewpoint of reaction rate.
  • the addition amount (use amount) of the catalyst is not particularly limited, but is usually preferably 1 to 3000 ppm, more preferably 50 to 1000 ppm, based on weight. When the addition amount of the catalyst is less than 1 ppm, a sufficient reaction rate may not be obtained. On the other hand, if it exceeds 3000 ppm, the physical properties of the product may be adversely affected.
  • the reaction of the above urethane isocyanate prepolymer and component (A) can proceed in the presence of a known volatile organic solvent. It does not specifically limit as a volatile organic solvent, for example, the volatile organic solvent etc. which were illustrated above can be used. Of these, ethyl acetate and butyl acetate are preferred from the viewpoints of boiling point and economy. In the above reaction, a volatile organic solvent may not be used.
  • a reactive diluent can be used instead of the volatile organic solvent.
  • a reactive diluent The below-mentioned (meth) acryloyl group containing monomer etc. can be used.
  • About the meaning of using a reactive diluent, the effect acquired, etc. are as above-mentioned.
  • reaction of the above-mentioned urethane isocyanate prepolymer and component (A) is not particularly limited, but preferably proceeds at a temperature of 130 ° C. or lower (reaction temperature), more preferably 50 to 130 ° C.
  • reaction temperature exceeds 130 ° C.
  • radical polymerization by heat proceeds to crosslink the double bond portion, and a gelled product may be generated.
  • reaction temperature is less than 50 ° C., a practically sufficient reaction rate may not be obtained.
  • the reaction of the above urethane isocyanate prepolymer and component (A) is usually carried out until the isocyanate group concentration (residual isocyanate group concentration) is 0.1% by weight or less.
  • the method for measuring the isocyanate group concentration is as described above.
  • the urethane (meth) acrylate of the present invention obtained by the above production method can be used as it is (for example, an active energy ray-curable urethane (meth) acrylate composition as it is in a composition containing a volatile organic solvent). And can be used after purification.
  • purification of the urethane (meth) acrylate of the present invention known or conventional methods can be used, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc. Separation means combining the above can be used.
  • the urethane (meth) acrylate of the present invention is obtained by reacting a lactone-modified hydroxyl group-containing poly (meth) acrylate (A) with an isocyanate compound (B) (including component (B1)), and the component (
  • A) is a compound represented by the formula (2)
  • the urethane (meth) acrylate of the present invention is represented by the following formula (3).
  • R 1 , R 2 , R 3 , p, and q are the same as those in formula (1) and formula (2), respectively.
  • R 4 is a group (residue) formed by removing the isocyanate group on the structural formula from the isocyanate compound (B) (compound having r isocyanate groups), for example, r Valent hydrocarbon group (for example, linear, branched or cyclic aliphatic hydrocarbon group; aromatic hydrocarbon group, etc.), r-valent heterocyclic group, hydrocarbon group and heterocyclic group bonded And r-valent groups (specifically, groups formed by excluding isocyanate groups on the structural formula from the above-exemplified isocyanate compound (B)) and the like.
  • r represents an integer of 1 or more.
  • the urethane (meth) acrylate of the present invention is obtained by reacting a lactone-modified hydroxyl group-containing poly (meth) acrylate (A), an isocyanate compound (B1), and a polyol (C), the urethane (meth) ) Acrylate is represented by the following formula (4).
  • R 1 , R 2 , R 3 , p, and q are the same as those in formula (1) and formula (2), respectively.
  • R 5 is an isocyanate on the structural formula from a urethane isocyanate prepolymer (urethane prepolymer having s number of isocyanate groups) obtained by reacting the isocyanate compound (B1) with the polyol (C). A group (residue) formed by removing a group. s represents an integer of 2 or more.
  • the active energy ray-curable urethane (meth) acrylate composition of the present invention is a composition containing the urethane (meth) acrylate of the present invention as an essential curing component (curable component) (active energy ray-curable resin composition). It is.
  • the active energy ray-curable urethane (meth) acrylate composition of the present invention can be used alone or in combination of two or more. it can.
  • the content (blending amount) of the urethane (meth) acrylate of the present invention in the active energy ray-curable urethane (meth) acrylate composition of the present invention is not particularly limited, but the active energy ray-curable urethane (meth) acrylate composition is not limited.
  • the total amount (100% by weight) is preferably 30% by weight or more (eg, 30 to 99% by weight), more preferably 50 to 98% by weight, and still more preferably 55 to 90% by weight.
  • the active energy ray-curable urethane (meth) acrylate composition of the present invention may contain a photopolymerization initiator (photoinitiator).
  • a photopolymerization initiator photoinitiator
  • photopolymerization initiators known or conventional photoradical polymerization initiators can be used, and are not particularly limited.
  • photopolymerization initiators 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1- ON, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether , Benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl Ether, benzoin phenyl ether, benzyldimethyl ketal, be
  • the content (blending amount) of the photopolymerization initiator is not particularly limited, but is preferably 1 to 10% by weight with respect to the total amount (100% by weight) of the active energy ray-curable urethane (meth) acrylate composition, The amount is preferably 1 to 5% by weight, more preferably about 3% by weight (for example, 2 to 4% by weight).
  • the curing rate tends to be faster.
  • the content of the photopolymerization initiator is 10% by weight or less, a cured product having a high curing rate and excellent physical properties tends to be obtained.
  • the content of the photopolymerization initiator exceeds 10% by weight, the curing rate is not further improved, and the physical properties of the cured product tend to be impaired.
  • the active energy ray-curable urethane (meth) acrylate composition of the present invention is a compound having a (meth) acryloyl group other than this ("(meth) acryloyl group-containing monomer" and Preferably).
  • the (meth) acryloyl group-containing monomer is a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group per molecule.
  • the (meth) acryloyl group-containing monomer a known or commonly used compound (monomer) having a (meth) acryloyl group can be used, and is not particularly limited, but is not limited to phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate.
  • examples of the (meth) acryloyl group-containing monomer include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, and unsaturated. Examples thereof include oligomers such as polyester.
  • the (meth) acryloyl group-containing monomer can be used alone or in combination of two or more. .
  • the content (blending amount) of the (meth) acryloyl group-containing monomer in the active energy ray-curable urethane (meth) acrylate composition of the present invention is not particularly limited, but is 100 parts by weight of the urethane (meth) acrylate of the present invention.
  • the amount is preferably 1 to 1000 parts by weight, more preferably 1 to 500 parts by weight, and still more preferably 1 to 100 parts by weight.
  • the content is less than 1 part by weight, there is no meaning to add as a solvent, and when it exceeds 1000 parts by weight, the characteristics due to the use of the urethane (meth) acrylate of the present invention tend not to appear.
  • Organic solvent An organic solvent or the like may be added to the active energy ray-curable urethane (meth) acrylate composition of the present invention for viscosity adjustment, if necessary.
  • organic solvent known or conventional organic solvents can be used and are not particularly limited, but ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, and methoxyethyl acetate Solvents; ether solvents such as diethyl ether, ethylene glycol methyl ether and dioxane; aromatic solvents such as toluene and xylene; aliphatic solvents such as pentane and hexane; halogen solvents such as methylene chloride, chlorobenzene and chloroform; isopropanol, Examples include alcohol solvents such as butanol.
  • the organic solvent can be used alone or in combination of two or more.
  • the content (blending amount) of the organic solvent is not particularly limited, but is preferably 0 to 30% by weight with respect to the total amount (100% by weight) of the active energy ray-curable urethane (meth) acrylate composition.
  • additives can be blended in the active energy ray-curable urethane (meth) acrylate composition of the present invention.
  • known or commonly used additives can be used, and are not particularly limited.
  • one type of additive can be used alone, or two or more types can be used in combination.
  • the content (blending amount) of the additive is not particularly limited, but is preferably 0 to 10% by weight, more preferably 0.8% with respect to the active energy ray-curable urethane (meth) acrylate composition (100% by weight). 05 to 5% by weight.
  • the active energy ray-curable urethane (meth) acrylate composition of the present invention is obtained by mixing the urethane (meth) acrylate of the present invention and other components such as a photopolymerization initiator and an organic solvent as necessary.
  • mixing means known or commonly used means can be used, and is not particularly limited.
  • means such as various mixers such as a dissolver and a homogenizer, kneaders, rolls, bead mills, self-revolving stirrers and the like can be used.
  • conditions, such as temperature and the rotation speed in the case of mixing are not specifically limited, It can set suitably.
  • cured product of the present invention By curing the active energy ray-curable urethane (meth) acrylate composition of the present invention by active energy ray irradiation, a cured product (sometimes referred to as “cured product of the present invention”) is obtained.
  • the cured product of the present invention has a balance between high surface hardness (for example, abrasion resistance and scratch resistance) and curl resistance.
  • the active energy ray-curable urethane (meth) acrylate composition of the present invention is applied to an object to form a coating film, and then irradiated with active energy rays such as ultraviolet rays and electron beams. Cure to give a cured coating.
  • the light source for performing ultraviolet irradiation is not particularly limited, and for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like is used.
  • the irradiation time of ultraviolet rays varies depending on the type of light source, the distance between the light source and the coating surface, other conditions, and the like, but it is several tens of seconds at most, usually several seconds.
  • the irradiation with ultraviolet rays it is possible to complete the curing by heating as necessary.
  • electron beam irradiation although not particularly limited, for example, an electron beam having an energy in the range of 50 to 1000 KeV is used, and the irradiation dose is preferably 2 to 5 Mrad.
  • an irradiation source with a lamp output of about 80 to 300 W / cm is used.
  • the thickness of the cured coating film is not particularly limited, but is usually about 50 to 300 ⁇ m.
  • the active energy ray-curable urethane (meth) acrylate composition of the present invention is used, for example, for forming a cured coating film on the surface of an article, specifically, a coating agent (coating use), a paint (coating use), and adhesion. It can be preferably used for an agent (adhesive use).
  • the cured coating film formed from the active energy ray-curable urethane (meth) acrylate composition of the present invention has a high surface hardness, so it has excellent surface protection of the object (article) and also has curl resistance. Since it is excellent, a high quality product can be obtained without causing problems such as curling of the object.
  • the object (application object) to which the active energy ray-curable urethane (meth) acrylate composition of the present invention is applied is not particularly limited, but for example, polyethylene terephthalate (PET), polymethacrylate, polycarbonate, Articles made of plastic such as vinyl chloride resin; those obtained by depositing metal on the plastic surface of the above articles; wood; metal plates; various articles such as paper.
  • the shape of the object (application object) is not particularly limited. The above-mentioned plastics, wood, metal, paper, etc.
  • the active energy ray-curable urethane (meth) acrylate composition of the present invention in which the active energy ray-curable urethane (meth) acrylate composition of the present invention is used as a coating or an adhesive are various building materials, furniture, printing paper, can products, It is useful in various products such as home appliances and digital video discs (DVD).
  • the active energy ray-curable urethane (meth) acrylate composition of the present invention is excellent in hydrolysis resistance, and the formed coating film or adhesive is also excellent in flexibility and adhesion.
  • Synthesis example 1 [Synthesis of lactone-modified polyfunctional acrylic compound (lactone polymer (1))]
  • a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube and condenser 342.2 g of pentaerythritol (tri / tetra) acrylate (trade name “Aronix M305”, manufactured by Toagosei Co., Ltd.), ⁇ Caprolactone (trade name “Placcel M”, manufactured by Daicel Corporation) 157.4 g, 4-methoxyphenol (produced by Kawaguchi Chemical Co., Ltd.) 0.36 g (720 ppm), and octylate tin (trade name “Stanocto”), 0.055 g (110 ppm) (manufactured by API Corporation) was charged.
  • pentaerythritol (tri / tetra) acrylate trade name “Aronix M305”, manufactured by Toagosei Co., Ltd.
  • FIG. 1 shows a chart of 1 H-NMR spectrum of the above product (solvent: deuterated chloroform).
  • Synthesis example 2 [Synthesis of lactone-modified polyfunctional acrylic compound (lactone polymer (2))]
  • a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube, and condenser pentaerythritol (tri / tetra) acrylate (trade name “Aronix M305”, manufactured by Toagosei Co., Ltd.) 232.4 g, ⁇ 267.2 g of caprolactone (trade name “Placcel M”, manufactured by Daicel Corporation), 0.36 g (720 ppm) of 4-methoxyphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.), and tin octylate (trade name “Stanocto”), 0.055 g (110 ppm) (manufactured by API Corporation) was charged, and this mixture remained at 130 ° C.
  • FIG. 2 shows a chart of 1 H-NMR spectrum of the above product (solvent: deuterated chloroform).
  • the reaction is continued until the amount of ⁇ -caprolactone is less than 1% by weight (the amount charged is 100% by weight) by GC analysis.
  • a boxy product was obtained.
  • the obtained product is a mixture of pentaerythritol triacrylate, a modified ⁇ -caprolactone (lactone polymer (3); corresponding to the above-mentioned component (A)) and pentaerythritol tetraacrylate. .3 mg KOH / g.
  • the trade name “Aronix M305” is a mixture of pentaerythritol triacrylate (tri) and pentaerythritol tetraacrylate (tetra), and the ratio (weight basis) is 60:40 (tri: tetra). is there. That is, the number of moles of ⁇ -caprolactone added to 1 mole of pentaerythritol triacrylate in Synthesis Example 1 is 2 moles, the number of moles of addition in Synthesis Example 2 is 5 moles, and the number of moles of addition in Synthesis Example 3 is 7 moles. Is a mole.
  • Example 1 Synthesis of Urethane Acrylate (UA1)]
  • a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube, and condenser 898 g of the product obtained in Synthesis Example 1, 1.0 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C. Next, 100 g of isophorone diisocyanate (manufactured by Evonik) was continuously added dropwise in 3 hours.
  • FIG. 3 shows a chart (solvent: deuterated chloroform) of 1 H-NMR spectrum of the obtained urethane acrylate (UA1). Moreover, the chart of IR spectrum of the obtained urethane acrylate (UA1) is shown in FIG. FIG.
  • urethane acrylate in UA1 (a component having a peak top retention time of 20.88 minutes) has a weight average molecular weight (Mw) of 2772, a number average molecular weight (Mn) of 1840, a molecular weight distribution ( Mw / Mn) was 1.51.
  • Example 2 Synthesis of Urethane Acrylate (UA2)]
  • a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube, and condenser 928 g of the product obtained in Synthesis Example 2, 1.0 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C. Next, 70 g of isophorone diisocyanate (manufactured by Evonik) was continuously added dropwise in 3 hours.
  • urethane acrylate (UA2) contains pentaerythritol tetraacrylate in addition to urethane acrylate (the urethane (meth) acrylate of the present invention).
  • FIG. 6 shows a chart (solvent: deuterated chloroform) of 1 H-NMR spectrum of the obtained urethane acrylate (UA2).
  • the chart of IR spectrum of the obtained urethane acrylate (UA2) is shown in FIG.
  • FIG. 8 shows a GPC elution curve of the obtained urethane acrylate (UA2).
  • urethane acrylate in UA2 (a component having a peak top retention time of 20.13 minutes) has a weight average molecular weight (Mw) of 4248, a number average molecular weight (Mn) of 2436, a molecular weight distribution ( Mw / Mn) was 1.74.
  • Example 3 Synthesis of Urethane Acrylate (UA3)]
  • a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube, and condenser 899 g of the product obtained in Synthesis Example 1, 1.0 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C. Next, 99 g of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK) was continuously added dropwise over 3 hours.
  • 2-acryloyloxyethyl isocyanate manufactured by Showa Denko KK
  • urethane acrylate (UA3) was obtained.
  • UA3 contains pentaerythritol tetraacrylate in addition to urethane acrylate (the urethane (meth) acrylate of the present invention).
  • Example 4 [Synthesis of Urethane Acrylate (UA4)] 129 g of isophorone diisocyanate (manufactured by Evonik) and 0.5 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.) are charged into a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction pipe and condenser. The temperature was raised to 60 ° C., and 290 g of a polyester polyol (trade name “Nipporan 4002”, manufactured by Nippon Polyurethane Industry Co., Ltd.) was continuously added dropwise over 2 hours.
  • a polyester polyol trade name “Nipporan 4002”, manufactured by Nippon Polyurethane Industry Co., Ltd.
  • urethane acrylate contains pentaerythritol tetraacrylate in addition to urethane acrylate (the urethane (meth) acrylate of the present invention).
  • Example 5 Synthesis of Urethane Acrylate (UA5)]
  • a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube, and condenser was charged with 101 g of isophorone diisocyanate (Evonik) and 0.5 g of dibutyltin dilaurate (Nitto Kasei Co., Ltd.).
  • the temperature was raised to 60 ° C., and 228 g of a polyester polyol (trade name “Nipporan 4002”, manufactured by Nippon Polyurethane Industry Co., Ltd.) was continuously added dropwise over 2 hours.
  • a polyester polyol trade name “Nipporan 4002”, manufactured by Nippon Polyurethane Industry Co., Ltd.
  • urethane acrylate (UA5).
  • UA5 contains pentaerythritol tetraacrylate in addition to urethane acrylate (the urethane (meth) acrylate of the present invention).
  • Example 6 Synthesis of Urethane Acrylate (UA6)]
  • a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube, and condenser 839 g of the product obtained in Synthesis Example 1, 0.5 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C.
  • 160 g of hexamethylene diisocyanate trimer trade name “Takenate D-170N”, manufactured by Mitsui Chemicals, Inc.
  • urethane acrylate (UA6).
  • pentaerythritol tetraacrylate is contained in addition to urethane acrylate (urethane (meth) acrylate of the present invention).
  • Example 7 Synthesis of Urethane Acrylate (UA7)]
  • a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube, and condenser 884 g of the product obtained in Synthesis Example 2, 0.5 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C.
  • 114 g of hexamethylene diisocyanate trimer (trade name “Takenate D-170N”, manufactured by Mitsui Chemicals, Inc.) was continuously added dropwise over 3 hours.
  • urethane acrylate (UA7).
  • UA7 includes pentaerythritol tetraacrylate in addition to urethane acrylate (the urethane (meth) acrylate of the present invention).
  • UA1 Reaction product of lactone polymer (1) and isophorone diisocyanate (IPDI)
  • UA2 Reaction product of lactone polymer (2) and IPDI
  • UA3 Reaction product of lactone polymer (1) and 2-acryloyloxyethyl isocyanate
  • UA4 Reaction product of polyester diol, lactone polymer (1) and IPDI
  • UA5 Reaction product of polyester diol, lactone polymer (2) and IPDI
  • UA6 Reaction product of lactone polymer (1) and hexamethylene diisocyanurate (HDI nurate)
  • UA7 Reaction product of lactone polymer (2) and HDI nurate
  • UA8 Reaction product of pentaerythritol triacrylate
  • IPDI UA9 Reaction product of monomer acrylated with lactone-modified product of pentaerythritol and IPDI UA10: Lactone polymer 3) a reaction product of IPDI
  • Examples 8 to 20, Comparative Examples 4 to 7 [Preparation of active energy ray-curable urethane (meth) acrylate composition] While stirring and mixing with a stainless steel beaker using a stirring motor, the components shown in Table 1 are sequentially added in the proportions shown in Table 1 to obtain each composition (active energy ray-curable urethane (meth) acrylate composition). It was.
  • a Taber abrasion test was carried out by the following procedure using the sample.
  • ASTM D-1044 using a Taber abrasion tester (manufactured by Yasuda Seiki Seisakusyo Co., Ltd.), wear the cured coating film on the above sample under the conditions of wear wheel CS-10F, load 500 g, rotation speed 300 cycles. I let you.
  • the cured coating film on the sample is washed, and the haze of the sample (this is referred to as “post-wear haze”) is measured with a haze meter (trade name “HAZE METER NDH2000”, manufactured by Nippon Denshoku Co., Ltd.).
  • Step wool resistance First, the same sample as that prepared in the Taber abrasion test was prepared. Using the sample, steel wool resistance (scratch resistance) was evaluated by the following procedure. About the surface of the cured coating film in the sample, the 60 ° gloss before the test was measured with a gloss meter, and then the surface of the cured coating film was rubbed 100 times with a load of 1 kg / cm 2 using # 0000 steel wool. . After the test, the 60 ° gloss at the rubbing part (60 ° gloss after the test) was measured in the same manner as before the test, and the gloss retention was calculated by the following formula. Based on the gloss retention value, steel wool resistance was evaluated according to the following criteria.
  • the active energy ray-curable urethane (meth) acrylate composition obtained above was converted into a 100 ⁇ m thick polyethylene terephthalate film (PET film; trade name “O321E”, Mitsubishi Plastics Co., Ltd.) using wire bar # 4. (Made; length: 10 cm ⁇ width: 10 cm). Thereafter, the composition was cured by ultraviolet irradiation (5 m / min ⁇ 2 kW, irradiation distance 11 cm, number of times of irradiation twice, integrated light quantity 900 mJ / cm 2 ), and the resulting PET film / cured product laminate was used as a sample. Using.
  • PETIA Trade name “PETIA” (pentaerythritol (tri / tetra) acrylate), manufactured by Daicel Ornex Co., Ltd.
  • IRR214K Trade name “IRR214K” (tricyclodecane dimethanol diacrylate), manufactured by Daicel Ornex Co., Ltd.
  • TPGDA Product name “TPGDA” (Tripropylene glycol diacrylate), manufactured by Daicel Ornex Co., Ltd.
  • DPHA Product name “DPHA” (dipentaerythritol hexaacrylate), manufactured by Daicel Ornex Co., Ltd.
  • Irg184 Product name “IRGACURE184” (Photoinitiator: 1-hydroxycyclohexyl phenyl ketone), manufactured by BASF
  • the urethane (meth) acrylate of the present invention and the active energy ray-curable urethane (meth) acrylate composition containing the urethane (meth) acrylate are used, for example, in paint applications, coating applications, adhesive applications, etc. (for example, paints, coating agents, adhesives, etc.
  • paint applications, coating applications, adhesive applications, etc. for example, paints, coating agents, adhesives, etc.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne du (méth)acrylate d'uréthane obtenu en faisant réagir un poly(méth)acrylate (A) contenant un groupe hydroxyle modifié par une lactone comportant de 1 à 6 moles de lactone ajoutée par mole de poly(méth)acrylate d'hydroxyalkyle, et un composé isocyanate (B) comprenant un ou plusieurs groupes isocyanate par molécule, ledit (méth)acrylate d'uréthane étant utilisé comme matériau avec lequel il est possible de former un film de revêtement (film de revêtement durci) doté d'un bon équilibre entre à la fois une dureté de surface élevée (par exemple une résistance à l'abrasion et une résistance aux rayures) et une résistance au tuilage.
PCT/JP2015/081595 2014-12-08 2015-11-10 (méth)acrylate d'uréthane, composition de (méth)acrylate d'uréthane durcissable par un rayonnement d'énergie active et article durci associé WO2016093005A1 (fr)

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CN112300306A (zh) * 2020-11-09 2021-02-02 广东石油化工学院 一种生物降解性可辐射固化的（甲基）丙烯酸酯及其制备方法

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KR101979784B1 (ko) * 2017-07-05 2019-05-20 전남대학교산학협력단 Uv 경화용 코팅제 및 그 제조방법

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JP2003137964A (ja) * 2001-11-02 2003-05-14 Daicel Ucb Co Ltd 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
JP2004035599A (ja) * 2002-06-28 2004-02-05 Natoko Kk ウレタン（メタ）アクリレート及びそれを含有する活性エネルギー線硬化性組成物並びにそれらの用途
JP2007314768A (ja) * 2006-04-27 2007-12-06 Hitachi Chem Co Ltd 光硬化性樹脂組成物及び光硬化性塗料

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JP2003137964A (ja) * 2001-11-02 2003-05-14 Daicel Ucb Co Ltd 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
JP2004035599A (ja) * 2002-06-28 2004-02-05 Natoko Kk ウレタン（メタ）アクリレート及びそれを含有する活性エネルギー線硬化性組成物並びにそれらの用途
JP2007314768A (ja) * 2006-04-27 2007-12-06 Hitachi Chem Co Ltd 光硬化性樹脂組成物及び光硬化性塗料

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112300306A (zh) * 2020-11-09 2021-02-02 广东石油化工学院 一种生物降解性可辐射固化的（甲基）丙烯酸酯及其制备方法
CN112300306B (zh) * 2020-11-09 2022-03-29 广东石油化工学院 一种生物降解性可辐射固化的(甲基)丙烯酸酯及其制备方法

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