Curable polyurethane resin composition, cured product, and laminate

Abstract

A curable polyurethane resin composition contains a reaction product of a polyisocyanate component containing an aliphatic diisocyanate and / or a derivative thereof, and a hydroxyl component containing: a heterocycle-containing polyhydric alcohol from a plant, the polyhydric alcohol containing a heterocycle structure and being from a plant; and a hydroxyl group-containing unsaturated compound containing an ethylenic unsaturated group and a hydroxyl group.

Description

TECHNICAL FIELD

[0001] The present application relates to a curable polyurethane resin composition, a cured product, and a laminate, and particularly to a curable polyurethane resin composition which is cured by irradiation of active energy rays, a cured product thereof, and a laminate provided with a cured film formed from the cured product thereof. BACKGROUND

[0002] Urethane acrylates have been used in a wide range of fields such as coating materials, inks, adhesives, and bonding agents for various industrial products.

[0003] In recent years, in such urethane acrylates, in order to reduce environmental load, the use of raw materials from plants has been studied.

[0004] For example, a curable polyurethane resin composition containing a urethane resin obtained by reacting a polyisocyanate containing pentamethylene diisocyanate and / or a derivative thereof from plants, a polyol, and a hydroxyl group-containing unsaturated compound containing an ethylenic unsaturated group and a hydroxyl group has been proposed (for example, see Patent Document 1).

[0005] PRIOR ART DOCUMENTS

[0006] PATENT DOCUMENTS

[0007] Patent Document 1: Japanese Patent Application Publication No. 2016-190948 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] In Patent Document 1, after further compounding a polyfunctional (meth)acrylate in the curable polyurethane resin composition, active energy rays are irradiated to crosslink the urethane resin, thereby obtaining a cured product.

[0010] However, in the curable polyurethane resin composition, depending on the type of the polyol, when a polyfunctional (meth)acrylate is compounded in the curable polyurethane resin composition, the compatibility of the polyfunctional (meth)acrylate with the urethane resin is insufficient, and there is a problem that turbidity occurs in the obtained cured product.

[0011] The present application is a curable polyurethane resin composition capable of suppressing turbidity, a cured product thereof, and a laminate provided with a cured film formed from the cured product thereof.

[0012] MEANS FOR SOLVING THE PROBLEMS

[0013] The present invention [1] is a curable polyurethane resin composition comprising a reaction product of a polyisocyanate component and a hydroxyl component, wherein the polyisocyanate component comprises an aliphatic diisocyanate and / or its derivatives, and the hydroxyl component comprises: a heterocyclic polyol derived from a plant, wherein the polyol contains a heterocyclic structure and is derived from a plant; and a hydroxyl-containing unsaturated compound, wherein the hydroxyl-containing unsaturated compound contains an olefinic unsaturated group and a hydroxyl group.

[0014] The present invention [2] includes the curable polyurethane resin composition described in [1] above, wherein the aforementioned aliphatic diisocyanate comprises 1,5-pentanediisocyanate derived from plants.

[0015] The present invention [3] includes the curable polyurethane resin composition described in [1] or [2] above, wherein the aforementioned heterocyclic plant-derived polyol is isosorbide-modified polycarbonate polyol.

[0016] The present invention [4] includes any one of the curable polyurethane resin compositions described in [1] to [3] above, and further comprises a polyfunctional (meth)acrylate having three or more olefinic unsaturated groups, and contains 30 or more of the aforementioned polyfunctional (meth)acrylate relative to 100 parts by mass of the aforementioned reaction product.

[0017] The present invention [5] includes the cured product of the curable polyurethane resin composition described in any one of [1] to [4] above.

[0018] The present invention [6] includes the cured product described in [5] above, having a haze of less than 0.5%.

[0019] The present invention [7] includes a laminate having a coated body and a cured film formed from the cured material described in [5] or [6] in the thickness direction.

[0020] Invention Effects

[0021] The curable polyurethane resin composition of the present invention contains a heterocyclic polyol derived from a plant (which contains a heterocyclic structure and is derived from a plant) as the polyol. Therefore, it is possible to reduce the environmental impact and suppress turbidity of the cured product obtained by curing the curable polyurethane resin composition. As a result, in the cured product of the present invention and in the laminate of the present invention having a cured film formed from the cured product, it is possible to reduce the environmental impact and suppress turbidity of the cured film. Attached Figure Description

[0022] [ Figure 1 ] Figure 1 This is a schematic diagram illustrating one embodiment of the method for manufacturing the laminate of the present invention. Figure 1 A shows the first step in preparing the object to be painted. Figure 1B shows a second step of arranging the cured film on one face in the thickness direction of the coated body. DETAILED DESCRIPTION

[0023] The curable polyurethane resin composition of the present application contains a reaction product of a polyisocyanate component and a hydroxyl component. The reaction product is a urethane resin. In detail, the hydroxyl component contains a hydroxyl group-containing unsaturated compound, and therefore, the reaction product is a reactive energy ray-curable urethane resin.

[0024] < Polyisocyanate component >

[0025] The polyisocyanate component contains an aliphatic diisocyanate and / or a derivative thereof.

[0026] As the aliphatic diisocyanate, for example, hexamethylene diisocyanate (hexane diisocyanate) (HDI), pentamethylene diisocyanate (pentane diisocyanate) (PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3- or 1,3-butane diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate can be mentioned.

[0027] As the hexamethylene diisocyanate, for example, 1,2-hexane diisocyanate, 1,3-hexane diisocyanate, 1,4-hexane diisocyanate, 1,5-hexane diisocyanate, 1,6-hexane diisocyanate, and 2,5-hexane diisocyanate can be mentioned, and preferably, 1,6-hexane diisocyanate can be mentioned.

[0028] As the pentamethylene diisocyanate, for example, 1,5-pentane diisocyanate, 1,4-pentane diisocyanate, and 1,3-pentane diisocyanate can be mentioned, and preferably, 1,5-pentane diisocyanate can be mentioned.

[0029] As the aliphatic diisocyanate, preferably, hexamethylene diisocyanate and pentamethylene diisocyanate can be mentioned, more preferably, pentamethylene diisocyanate can be mentioned, and further preferably, 1,5-pentane diisocyanate can be mentioned.

[0030] In addition, 1,5-pentane diisocyanate is particularly preferably derived from plants. The 1,5-pentane diisocyanate derived from plants can be obtained by an enzyme-based decarboxylation reaction of lysine. The method for producing such 1,5-pentane diisocyanate derived from plants is described in the specification of International Publication Brochure No. WO2012 / 121291.

[0031] In addition, the biomass degree of such 1,5-pentane diisocyanate is, for example, 10% or more, preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and in addition, for example, 80% or less.

[0032] Note that the method for calculating the biomass degree is described in detail in the Examples described later (hereinafter, the same applies).

[0033] The aliphatic diisocyanate can be used alone or in combination with two or more kinds.

[0034] As the derivative of the aliphatic diisocyanate, for example, a polymer (e.g., a dimer, a trimer (e.g., an isocyanurate derivative, an iminooxadiazinedione derivative), a pentamer, a heptamer, etc.) of the above-mentioned aliphatic diisocyanate, a uretonimine derivative (e.g., a uretonimine derivative generated by the reaction of the above-mentioned aliphatic diisocyanate with a monohydric alcohol or a dihydric alcohol), a polyol derivative (e.g., a polyol derivative (alcohol adduct) generated by the reaction of the above-mentioned aliphatic diisocyanate with a trihydric alcohol (e.g., trimethylolpropane), etc.), a biuret derivative (e.g., a biuret derivative generated by the reaction of the above-mentioned aliphatic diisocyanate with water or an amine, etc.), a urea derivative (e.g., a urea derivative generated by the reaction of the above-mentioned aliphatic diisocyanate with a diamine, etc.), an oxadiazinedione derivative (e.g., an oxadiazinedione generated by the reaction of the above-mentioned aliphatic diisocyanate with carbon dioxide, etc.), a carbodiimide derivative (a carbodiimide derivative generated by decarboxylative condensation of the above-mentioned aliphatic diisocyanate, etc.), a uretdione derivative, and a uretoneimine derivative can be mentioned, preferably an isocyanurate derivative can be mentioned, more preferably an isocyanurate derivative of pentamethylene diisocyanate can be mentioned, further preferably an isocyanurate derivative of 1,5-pentanediisocyanate can be mentioned, and particularly preferably an isocyanurate derivative of 1,5-pentanediisocyanate derived from a plant can be mentioned.

[0035] The biomass degree of the isocyanurate derivative of 1,5-pentanediisocyanate derived from a plant is, for example, 10% or more, preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and additionally, for example, 80% or less.

[0036] The derivative of the aliphatic diisocyanate can be used alone or in combination with two or more kinds.

[0037] The polyisocyanate component can further contain other polyisocyanates and / or derivatives thereof.

[0038] As the other polyisocyanate, for example, an aromatic diisocyanate, an aromatic aliphatic diisocyanate, and an alicyclic diisocyanate can be mentioned.

[0039] As the aromatic diisocyanate, for example, 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 2,4- or 2,6-toluene diisocyanate or a mixture thereof (TDI), o-dimethylbenzidine diisocyanate, 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, and 4,4'-diphenyl ether diisocyanate can be mentioned.

[0040] As the aromatic aliphatic diisocyanate, xylene diisocyanate (1,2-, 1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), and ω,ω'-diisocyanato-l,4-diethylbenzene can be mentioned.

[0041] As the alicyclic diisocyanate, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate) or a mixture thereof (H 12 MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate can be mentioned.

[0042] As the other polyisocyanate derivative, the derivative mentioned in the above-mentioned derivative of the aliphatic diisocyanate can be mentioned.

[0043] The blending ratio of the other polyisocyanate and the derivative thereof is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and, for example, 20 parts by mass or less, relative to 100 parts by mass of the polyisocyanate component.

[0044] The other polyisocyanate and the derivative thereof can be used alone or in combination of two or more.

[0045] The polyisocyanate component preferably contains the aliphatic diisocyanate and / or the derivative thereof, and does not contain the other polyisocyanate and the derivative thereof, more preferably does not contain the derivative of the aliphatic diisocyanate, and contains the aliphatic diisocyanate, or contains the aliphatic diisocyanate and the derivative of the aliphatic diisocyanate.

[0046] In the case where the polyisocyanate component contains an aliphatic diisocyanate and a derivative of the aliphatic diisocyanate, the content ratio of the aliphatic diisocyanate is, for example, 60 parts by mass or more, preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and, for example, 90 parts by mass or less, relative to 100 parts by mass of the total amount of the aliphatic diisocyanate and the derivative of the aliphatic diisocyanate. In addition, the content ratio of the derivative of the aliphatic diisocyanate is, for example, 10 parts by mass or more, and, for example, 40 parts by mass or less, preferably 30 parts by mass or less, more preferably 20 parts by mass or less.

[0047] Further, it is particularly preferable that the polyisocyanate component contain no derivative of an aliphatic diisocyanate and contain an aliphatic diisocyanate. Thereby, the turbidity of a cured product obtained by curing the curable polyurethane resin composition can be further suppressed.

[0048] [Hydroxyl component]

[0049] The hydroxyl component contains a heterocycle-containing polyol from plants and a hydroxyl group-containing unsaturated compound.

[0050] [Heterocycle-containing polyol from plants]

[0051] The heterocycle-containing polyol from plants is a polyol from plants having one or more heterocycles in the molecule.

[0052] As such a heterocycle-containing polyol from plants, for example, a polyol containing a structural unit derived from a dihydroxy compound represented by the following formula (1) can be given.

[0053] [Chemical formula 1]

[0054] Chemical formula 1

[0055]

[0056] As the dihydroxy compound represented by the above formula (1), for example, isosorbide, isomannide, and isoidide as structural isomers can be given, and preferably isosorbide can be given.

[0057] In addition, the dihydroxy compound represented by the above formula (1) is a component from plants.

[0058] In addition, the polyol can further contain a structural unit derived from another dihydroxy compound.

[0059] As the structural unit derived from another dihydroxy compound, for example, a structural unit derived from an aliphatic dihydroxy compound and a structural unit derived from an alicyclic dihydroxy compound (excluding the structural unit derived from the dihydroxy compound represented by the above formula (1). The same applies hereinafter.) can be given.

[0060] Examples of aliphatic dihydroxy compounds include linear aliphatic dihydroxy compounds and branched aliphatic dihydroxy compounds. Examples of linear aliphatic dihydroxy compounds include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol. Examples of branched aliphatic dihydroxy compounds include 1,2-propanediol, 1,3-butanediol, 1,2-butanediol, neopentanediol, and hexanediol.

[0061] Examples of alicyclic dihydroxy compounds include 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol, tricyclodecanediethanol, pentacyclopentadecanedimethanol, 2,6-decahydronaphthalenediethanol, 1,5-decahydronaphthalenediethanol, 2,3-decahydronaphthalenediethanol, 2,3-norbornanediethanol, 2,5-norbornanediethanol, and 1,3-adamantanediethanol.

[0062] Furthermore, among the polyols containing structural units from the dihydroxy compound shown in formula (1) above, the polyols are preferably macromolecular polyols.

[0063] The macromolecular polyol is a high molecular weight polyol with a number average molecular weight of 250 or more, preferably 400 or more, and for example, less than 10,000.

[0064] Examples of macromolecular polyols include polyester polyols, polycaprolactone polyols, polyether polyols, polycarbonate polyols, acrylic polyols, and urethane-modified polyols, with polycarbonate polyols being a preferred example.

[0065] Such polycarbonate polyols can be obtained by transesterification of a dihydroxy component with a carbonate diester (e.g., diphenyl carbonate), the dihydroxy component comprising: a dihydroxy compound containing structural units from the dihydroxy compound shown in formula (1) above; and a dihydroxy compound containing structural units from other dihydroxy compounds, as needed.

[0066] The polycarbonate polyol has a heterocyclic structure and contains structural units derived from the dihydroxy compound of formula (1) above, which is a plant-derived component. Therefore, the polycarbonate polyol has a heterocyclic structure and is derived from a plant.

[0067] In addition, as described above, the dihydroxy compound represented by the above formula (1) is preferably isosorbide. Thus, the polycarbonate polyol is preferably an isosorbide-modified polycarbonate polyol. That is, as the heterocycle-containing polyol from plants, an isosorbide-modified polycarbonate polyol is preferable. If the heterocycle-containing polyol from plants is an isosorbide-modified polycarbonate polyol, the environmental load can be further reduced.

[0068] The heterocycle-containing polyol from plants can be used alone or in combination with two or more kinds.

[0069] The biomass degree of the heterocycle-containing polyol from plants is, for example, 10% or more, preferably 30% or more, more preferably 40% or more, and, for example, 70% or less.

[0070] [Hydroxyl group-containing unsaturated compound]

[0071] The hydroxyl group-containing unsaturated compound has one or more ethylenically unsaturated groups and one or more hydroxyl groups in the molecule.

[0072] More specifically, the hydroxyl group-containing unsaturated compound has one or more groups containing an ethylenically unsaturated group selected from at least one of acryloyl group, methacryloyl group, vinylphenyl group, propenyl ether group, allyl ether group, and vinyl ether group, and one or more hydroxyl groups.

[0073] As the group containing an ethylenically unsaturated group, acryloyl group and / or methacryloyl group is preferable, and acryloyl group is further preferable.

[0074] Regarding the hydroxyl group-containing unsaturated compound, in the case where the group containing an ethylenically unsaturated group is acryloyl group and / or methacryloyl group, for example, a (meth)acrylate containing a hydroxyl group can be mentioned.

[0075] Note that, the term "(meth)acryl-" is defined as acryl- and / or methacryl-, and the term "(meth)acrylate" is defined as acrylate and / or methacrylate.

[0076] As the (meth)acrylate containing a hydroxyl group, for example, a monohydroxy mono(meth)acrylate having one hydroxyl group in one molecule and having one acryloyl group or methacryloyl group; for example, a polyhydroxy mono(meth)acrylate having a plurality of hydroxyl groups in one molecule and having one acryloyl group or methacryloyl group; for example, a monohydroxy poly(meth)acrylate having one hydroxyl group in one molecule and having a plurality of acryloyl groups and / or methacryloyl groups; and for example, a polyhydroxy poly(meth)acrylate having a plurality of hydroxyl groups in one molecule and having a plurality of acryloyl groups and / or methacryloyl groups can be mentioned.

[0077] As the monohydroxy mono(meth)acrylate, for example, (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 4-hydroxybutyl ester, (meth)acrylic acid 2-hydroxybutyl ester, (meth)acrylic acid 2-phenoxypropyl ester, (meth)acrylic acid 4-hydroxycyclohexyl ester, (meth)acrylic acid 3-chloro-2-hydroxypropyl ester, (meth)acrylic acid 2-hydroxy-3-phenyloxypropyl ester, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-hydroxyalkyl(meth)acryloyl phosphate, pentanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate can be given.

[0078] As the polyhydroxy mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, glycerol mono(meth)acrylate, and pentaerythritol mono(meth)acrylate can be given.

[0079] As the monohydroxy mono(meth)acrylate, for example, (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 4-hydroxybutyl ester, (meth)acrylic acid 2-hydroxybutyl ester, (meth)acrylic acid 2-phenoxypropyl ester, (meth)acrylic acid 4-hydroxycyclohexyl ester, (meth)acrylic acid 3-chloro-2-hydroxypropyl ester, (meth)acrylic acid 2-hydroxy-3-phenyloxypropyl ester, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-hydroxyalkyl(meth)acryloyl phosphate, pentanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate can be given.

[0080] As the polyhydroxy mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, glycerol mono(meth)acrylate, and pentaerythritol mono(meth)acrylate can be given.

[0081] As the polyhydroxy mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, glycerol mono(meth)acrylate, and pentaerythritol mono(meth)acrylate can be given.

[0082] As the polyhydroxy mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, glycerol mono(meth)acrylate, and pentaerythritol mono(meth)acrylate can be given.

[0083] As the polyhydroxy mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, glycerol mono(meth)acrylate, and pentaerythritol mono(meth)acrylate can be given.

[0084] As the hydroxyl group-containing unsaturated compound, in the case where the group containing an ethylenic unsaturated group is a vinyl ether group, for example, 2-hydroxyethyl vinyl ether and 2-hydroxypropyl vinyl ether can be given.

[0085] Among these hydroxyl group-containing unsaturated compounds, (meth)acrylates containing a hydroxyl group can be given, and monohydroxy mono(meth)acrylates can be further given, and 2-hydroxyethyl (meth)acrylate can be given even more, and 2-hydroxyethyl acrylate can be given in particular.

[0086] The hydroxyl group-containing unsaturated compound can be used alone or in combination of two or more.

[0087] Further, in order to allow the polyisocyanate component to react with the hydroxyl group component, the polyisocyanate component is mixed with the hydroxyl group component (the heterocycle-containing polyhydric alcohol derived from a plant and the hydroxyl group-containing unsaturated compound) and allowed to react.

[0088] Specifically, first, the polyisocyanate component is allowed to react with the heterocycle-containing polyhydric alcohol derived from a plant.

[0089] In detail, first, the polyisocyanate component is allowed to react with the heterocycle-containing polyhydric alcohol derived from a plant in a manner that the isocyanate groups (NCO) of the polyisocyanate component are in excess with respect to the hydroxyl groups (OH) of the heterocycle-containing polyhydric alcohol derived from a plant, thereby obtaining a prepolymer composition containing an isocyanate group-terminated prepolymer.

[0090] Specifically, the polyisocyanate component is allowed to react with the heterocycle-containing polyhydric alcohol derived from a plant in a manner that the equivalent ratio (NCO / OH) of the polyisocyanate component with respect to the heterocycle-containing polyhydric alcohol derived from a plant is, for example, 1.5 or greater, preferably 2 or greater, even more preferably 3 or greater, for example, 20 or less, preferably 10 or less, even more preferably 8 or less.

[0091] In the above reaction, the reaction temperature is, for example, 40°C or greater, preferably 50°C or greater, more preferably 60°C or greater, for example, 120°C or less, preferably 100°C or less, more preferably 90°C or less. In addition, the reaction time is, for example, 0.5 hours or greater, preferably 1 hour or greater, for example, 10 hours, preferably 5 hours or less.

[0092] The above reaction is ended at a point in time at which the desired isocyanate group concentration (for example, 1 mass% or greater and 40 mass% or less) is attained. In addition, the reaction is preferably performed under a nitrogen atmosphere. In addition, at the same time, in order to suppress polymerization (bulk polymerization) of the hydroxyl group-containing unsaturated compound, it is preferable to bubble dry air in the reaction liquid.

[0093] In addition, in the above reaction, if necessary, a known organic solvent and a known urethanization catalyst (for example, an amine-based catalyst, a tin-based catalyst, a lead-based catalyst, a bismuth-based catalyst, a zirconium-based catalyst, a zinc-based catalyst) can be added in an appropriate ratio.

[0094] Thus, a prepolymer composition which is a mixture of an isocyanate group-terminated prepolymer and unreacted polyisocyanate can be obtained.

[0095] In addition, in the above reaction, if an organic solvent is added, the prepolymer composition is prepared in the form of an organic solvent solution in which the isocyanate group-terminated prepolymer is dissolved or dispersed in the organic solvent.

[0096] Next, if necessary, unreacted polyisocyanate in the prepolymer composition is removed by, for example, a distillation method or an extraction method.

[0097] Next, the prepolymer composition is reacted with a hydroxyl group-containing unsaturated compound.

[0098] Thus, the hydroxyl group-containing unsaturated compound can be bonded to the molecular terminal of the isocyanate group-terminated prepolymer, and the molecular terminal of the urethane resin can contain an ethylenic unsaturated group.

[0099] Specifically, the isocyanate group-terminated prepolymer and unreacted polyisocyanate are reacted with the hydroxyl group-containing unsaturated compound in such a manner that the equivalent ratio (NCO / OH) of the isocyanate group (NCO) of the isocyanate group-terminated prepolymer and unreacted polyisocyanate to the hydroxyl group (OH) of the hydroxyl group-containing unsaturated compound becomes, for example, 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and 1.3 or less, preferably 1.2 or less, more preferably 1.1 or less.

[0100] In the above reaction, the reaction temperature is, for example, 40°C or more, preferably 60°C or more, and, for example, 100°C or less, preferably 80°C or less. The reaction time is, for example, 0.5 hours or more, and, for example, 10 hours or less.

[0101] In addition, in the above reaction, if necessary, the above reaction solvent and the above urethanization catalyst can be added in an appropriate ratio.

[0102] In addition, in the above reaction, in order to prevent polymerization (bulk polymerization) of the hydroxyl group-containing unsaturated compound, a polymerization inhibitor can also be added in an amount of 10 ppm or more, preferably 50 ppm or more, for example, 10,000 ppm or less, preferably 5,000 ppm or less, with respect to the reaction system.

[0103] As the polymerization inhibitor, for example, hydroquinone, methoxyphenol, methylhydroquinone (alias hydroquinone methyl ether), 2-tert-butylhydroquinone, p-benzoquinone, tert-butyl-p-benzoquinone, phenothiazine, and the like can be given.

[0104] In addition, in the above reaction, for example, a monohydric alcohol can be added.

[0105] As the monohydric alcohol, for example, methanol, ethanol, propanol, isopropanol, butanol, 1-methoxy-2-propanol, 2-ethylhexanol, other alkyl alcohol (C5 to 38) and aliphatic unsaturated alcohol (9 to 24), alkenyl alcohol, 2-propen-l-ol, alkadienyl alcohol (C6 to 8), and 3,7-dimethyl-l,6-octadien-3-ol can be given.

[0106] The monohydric alcohol is incorporated in a ratio of 1 or more than 1, more specifically, for example, 1 or more, preferably 1.05 or more, for example, 2 or less, preferably 1.5 or less, with respect to the unreacted isocyanate group.

[0107] In addition, the monohydric alcohol can be incorporated after the reaction of the prepolymer composition and the hydroxyl group-containing unsaturated compound is completed, or it can be mixed with the hydroxyl group-containing unsaturated compound and allowed to react with the prepolymer composition.

[0108] By incorporating the monohydric alcohol, the unreacted isocyanate group remaining at a prescribed concentration can be eliminated.

[0109] Thereby, for example, the urethane resin is obtained in the form of a mixture of the main product formed from the isocyanate group-terminated prepolymer and the hydroxyl group-containing unsaturated compound, and the by-product formed from the polyisocyanate and the hydroxyl group-containing unsaturated compound. Note that the above by-product can be removed as needed by, for example, a distillation method, an extraction method.

[0110] Note that in the urethane resin, the ethylenically unsaturated group can be contained in the molecular chain (midway portion), or it can be contained at the molecular terminal. The ethylenically unsaturated group is preferably contained at the molecular terminal of the urethane resin.

[0111] Note that the position of the ethylenically unsaturated group in the molecule of the urethane resin can be determined according to the molecular structure of the hydroxyl group-containing unsaturated compound.

[0112] In the case where the prepolymer composition is prepared in the form of an organic solvent solution, the urethane resin is prepared in the form of an organic solvent solution in which it is dissolved or dispersed.

[0113] The biomass degree of the urethane resin is, for example, 10% or more, preferably 40% or more, more preferably 45% or more, and, for example, 70% or less.

[0114] <Other embodiments of urethane resin>

[0115] The hydroxyl component can also contain other polyols other than the above-mentioned heterocycle-containing polyol from plants and the hydroxyl group-containing unsaturated compound, as needed.

[0116] As the other polyol, for example, the above-mentioned macromolecular polyol can be mentioned.

[0117] The blending ratio of the other polyol is not particularly limited and can be appropriately adjusted within a range in which the urethane resin has the above-mentioned biomass degree.

[0118] The other polyol can be used alone or in combination of two or more.

[0119] In addition, in the case where the hydroxyl component contains the other polyol, in order to make the polyisocyanate component react with the hydroxyl component, first, the polyisocyanate component is made to react with the heterocycle-containing polyol from plants and the other polyol, to obtain a prepolymer composition containing an isocyanate group-terminated prepolymer, and then, the prepolymer composition is made to react with the hydroxyl group-containing unsaturated compound.

[0120] The hydroxyl component is preferably composed of the heterocycle-containing polyol from plants and the hydroxyl group-containing unsaturated compound, without containing the other polyol.

[0121] <Curable polyurethane resin composition>

[0122] The curable polyurethane resin composition contains the above-mentioned urethane resin.

[0123] In addition, the curable polyurethane resin composition can also contain a multifunctional (meth)acrylate having three or more ethylenically unsaturated groups, depending on the purpose and use thereof.

[0124] That is, there are cases where a curable polyurethane resin composition containing a urethane resin without containing a multifunctional (meth)acrylate is first circulated, and then, a multifunctional (meth)acrylate is blended into the curable polyurethane resin composition. In addition, there are also cases where a curable polyurethane resin composition containing a urethane resin and a blended multifunctional (meth)acrylate is circulated.

[0125] The multifunctional (meth)acrylate is a compound that is polymerized by irradiation of active energy rays (described later). In addition, the multifunctional (meth)acrylate is also a reactive diluent that is blended in the case where the viscosity of the curable polyurethane resin composition is high.

[0126] In addition, the multifunctional (meth)acrylate contains three or more (meth)acryloyl groups as ethylenically unsaturated groups.

[0127] As the polyfunctional (meth) acrylate, for example, tri(meth) acrylate, tetra(meth) acrylate, penta(meth) acrylate, and hexa(meth) acrylate can be mentioned. As the tri(meth) acrylate, for example, trimethylolpropane tri(meth) acrylate, and pentaerythritol tri(meth) acrylate can be mentioned. As the tetra(meth) acrylate, for example, ditrimethylolpropane tetra(meth) acrylate, and pentaerythritol tetra(meth) acrylate can be mentioned. As the penta(meth) acrylate, for example, dipentaerythritol penta(meth) acrylate can be mentioned. As the hexa(meth) acrylate, for example, dipentaerythritol hexa(meth) acrylate can be mentioned.

[0128] As the polyfunctional (meth) acrylate, preferably, penta(meth) acrylate, hexa(meth) acrylate can be mentioned, more preferably, pentaerythritol penta(meth) acrylate, dipentaerythritol hexa(meth) acrylate can be mentioned, further preferably, pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate can be mentioned.

[0129] Further, among the polyfunctional (meth) acrylate, urethane (meth) acrylate obtained by reacting the above-mentioned polyfunctional (meth) acrylate with a polyisocyanate is also included. As the polyisocyanate, the above-mentioned diisocyanate exemplified in the polyisocyanate component can be mentioned. As such urethane (meth) acrylate, preferably, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer can be mentioned.

[0130] The blending ratio of the polyfunctional (meth) acrylate is 30 parts by mass or more, preferably 40 parts by mass or more, more preferably 50 parts by mass or more, further preferably 60 parts by mass or more, particularly preferably 70 parts by mass or more, most preferably 80 parts by mass or more, further 100 parts by mass or more, further 200 parts by mass or more, and for example, 400 parts by mass or less, relative to 100 parts by mass of the urethane resin (reaction product of the above-mentioned polyisocyanate component and the above-mentioned hydroxyl component).

[0131] If the blending ratio of the polyfunctional (meth) acrylate is the above-mentioned lower limit or more, the turbidity of the cured product obtained by curing the curable polyurethane resin composition can be suppressed, and the hardness of the cured product can be improved. In particular, if the blending ratio of the polyfunctional (meth) acrylate is 60 parts by mass or more, the turbidity of the cured product can be suppressed even after the abrasion resistance test described later.

[0132] The polyfunctional (meth) acrylate can be used alone or in combination of two or more. Preferably, the use of pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer alone, and the combination of pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate can be mentioned.

[0133] In addition, in the case where the curable polyurethane resin composition contains a polyfunctional (meth) acrylate having three or more ethylenically unsaturated groups, the curable polyurethane resin composition contains a known photopolymerization initiator as needed in an appropriate proportion.

[0134] In addition, in the curable polyurethane resin composition, various additives such as a sensitizer, a photopolymerization accelerator, an antifoaming agent, a leveling agent, a pigment, a dye, a silicon compound, a rosin, a silane coupling agent, an antioxidant, a colorant, a whitening agent, and the like can be added as needed in an appropriate proportion according to the purpose and use thereof.

[0135] The biomass degree of the curable polyurethane resin composition is, for example, 10% or more, preferably 30% or more, and more preferably 40% or more, and, for example, 70% or less.

[0136] <Effects>

[0137] The curable polyurethane resin composition contains a polyol from a plant (a polyol from a plant containing a heterocycle). Therefore, it is possible to reduce environmental load.

[0138] In addition, the curable polyurethane resin composition contains a polyol containing a heterocycle structure (a polyol from a plant containing a heterocycle). Therefore, it is possible to suppress turbidity of a cured product obtained by curing the curable polyurethane resin composition.

[0139] In particular, in the case where the curable polyurethane resin composition contains the above-described polyfunctional (meth) acrylate in a prescribed proportion, it is possible to suppress turbidity of the cured product.

[0140] In detail, if a polyol having a cyclic structure formed of a carbon ring is used, the compatibility with the polyfunctional (meth) acrylate decreases, and sometimes it is not possible to suppress turbidity of the cured product.

[0141] On the other hand, the curable polyurethane resin composition uses a polyol containing a heterocycle structure (a polyol from a plant containing a heterocycle). Therefore, electrostatic repulsion occurs between unpaired electrons of heteroatoms. It is inferred from this that the mutual overlapping of the cyclic structures is weaker than a carbon ring composed of only carbon atoms. It is inferred that because the mutual overlapping of the cyclic structures is weaker than a carbon ring composed of only carbon atoms, the compatibility with the polyfunctional (meth) acrylate is improved.

[0142] In addition, the ester group of the polyfunctional (meth) acrylate has polarity from a carbon-oxygen bond. On the other hand, it is inferred that because the heterocycle containing an element other than carbon has higher polarity than a carbon ring formed of only carbon atoms, the compatibility with the polyfunctional (meth) acrylate is improved.

[0143] The curable polyurethane resin composition can be used as, for example, a light molding resin used in a coating material, an ink, an adhesive, a sealant, an elastomer, a water-based resin, a thermosetting resin, a microcapsule, a dental material, a lens, a bonding resin, a waterproof material, a film, a sheet, a 3D printer, and the like, and in addition, as a piezoelectric material or a thermoelectric material used in a speaker, a sensor, a power generation device (a device for converting heat or a mechanical stimulus into electric energy), and the like.

[0144] For example, the coating material can be used for various industrial products such as a plastic film, a plastic sheet, a plastic foam, a spectacle lens, a spectacle frame, a fiber, artificial leather, synthetic leather, a metal, wood, and the like.

[0145] More specifically, the plastic film coating can be used for, for example, an optical member (for example, an optical film, an optical sheet, and the like), an optical coating material, a fiber, an electronic and electromechanical material, food packaging, cosmetic packaging, a decorative film, and a protective sheet for a solar cell module.

[0146] In addition, the adhesive and the sealant can be used for, for example, a display device such as a liquid crystal display (LCD), an EL (electroluminescence) display, EL lighting, electronic paper, a plasma display, and the like, and an information recording medium such as an optical disc (specifically, a Blu-ray disc, a DVD (digital video (or versatile) disc), an MO (magneto optical disc), a PD (phase change optical disc), and the like).

[0147] In addition, the ink can be used for, for example, flexographic printing, dry offset printing, intaglio printing such as letterpress printing, gravure printing such as gravure offset printing, lithographic printing such as offset printing, and hole block printing such as screen printing.

[0148]

[0149] By curing the curable polyurethane resin composition, a cured product can be obtained.

[0150] In order to cure the curable polyurethane resin composition, active energy rays are irradiated to the curable polyurethane resin composition.

[0151] As the active energy rays, for example, ultraviolet rays, electron rays, and the like can be given. The irradiation amount of the active energy rays is, for example, 50 mJ / cm 2 The above is preferably 100 mJ / cm 2 The above is, for example, 5000 mJ / cm 2 The below is preferably 1000 mJ / cm 2 The below.

[0152] ​Thus, a cured product can be obtained. Such a cured product can be obtained by curing the curable polyurethane resin composition. Therefore, environmental load is reduced, and haze is suppressed.

[0153] Specifically, the haze of the cured product is, for example, less than 0.5%, and preferably 0.4% or less.

[0154] The method for measuring the haze of the cured product is described in detail in the Examples described later.

[0155] In addition, since the cured product obtained by curing the curable polyurethane resin composition suppresses haze, it can be particularly suitably used in applications requiring transparency.

[0156] In the following description, as one example of the method for using the curable polyurethane resin composition, a case where the surface of a coated body 2 (described later) is coated with the curable polyurethane resin composition is described in detail.

[0157] <Method for using curable polyurethane resin composition (method for manufacturing laminate)>

[0158] The curable polyurethane resin composition can be used to coat the surface of the coated body 2. By coating the coated body 2, a laminate 1 can be manufactured.

[0159] The method for manufacturing the laminate 1 has the following steps: a first step of preparing the coated body 2; and a second step of applying the curable polyurethane resin composition to the surface (one face in the thickness direction) of the coated body 2 and curing it, thereby providing the cured film 3.

[0160] Reference Signs List Figure 1 One embodiment of the method for manufacturing the laminate 1 is described.

[0161] Figure 1 In the drawings, the paper surface up-down direction is the up-down direction (thickness direction), the paper surface upper side is the upper side (one side in the thickness direction), and the paper surface lower side is the lower side (the other side in the thickness direction). In addition, the paper surface left-right direction and the depth direction are face directions orthogonal to the up-down direction. Specifically, the direction arrows of the respective drawings are used as reference.

[0162] In the first step, as shown in Figure 1 A, the coated body 2 is prepared.

[0163] The coated body 2 is a coated body whose surface (one face in the thickness direction) is provided with various properties by the cured film 3.

[0164] Note that, Figure 1 In A, the coated body 2 has a flat plate shape, but the shape of the coated body 2 is not particularly limited, and various shapes can be selected.

[0165] As the coated body 2, there is no particular limitation, and examples that can be given include resins and metals.

[0166] In the second step, as shown in FIG. B, first, a curable polyurethane resin composition is applied to the surface (one face in the thickness direction) of the coated body 2, and dried as necessary, to form a coating film. Figure 1

[0167] Next, the coating film is cured. To cure the coating film, active energy rays are irradiated to the coating film.

[0168] Thus, the cured film 3 is disposed on the surface (one face in the thickness direction) of the coated body 2, to obtain the laminate 1.

[0169] Such a laminate 1 has, in the thickness direction, in order, the coated body 2, and the cured film 3 formed of the cured product of the curable polyurethane resin composition.

[0170] Since the laminate 1 has the cured film 3 formed of the cured product of the curable polyurethane resin composition, it is possible to reduce environmental load, and to suppress turbidity of the cured film 3.

[0171] Examples

[0172] Next, the present application will be described based on examples and comparative examples, but the present application is not limited to the following examples. Note that, unless otherwise specified, "parts" and "%" are based on mass. Also, in the following description, the specific values of the compounding ratio (content ratio), physical property values, parameters, etc. used can be replaced with the upper limit values (values defined in the form of "and below", "less than") or lower limit values (values defined in the form of "and above", "greater than") corresponding to the compounding ratio (content ratio), physical property values, parameters, etc. described in the "DETAILED DESCRIPTION" above.

[0173] 1. Details of ingredients

[0174] The trade names and abbreviations of the ingredients used in each production example, each example, and each comparative example will be described in detail.

[0175] 1,5-PDI: 1,5-pentamethylene diisocyanate, having a biomass degree of 70% according to ASTM D6866, trade name "STABiO PDI", manufactured by Mitsui Chemicals, Inc.

[0176] PDI uretonimine: isocyanuric acid ester derivative of 1,5-pentamethylene diisocyanate, having a biomass degree of 70% according to ASTM D6866, trade name "STABiO D-370N", manufactured by Mitsui Chemicals, Inc.

[0177] 1,6-HDI: 1,6-hexamethylene diisocyanate ​

[0178] HS0850H: polycarbonate polyol containing structural units derived from the above-mentioned dihydric compound represented by Formula (1) (derived from plants), hydroxyl value: 141.3 mgKOH / g, biomass degree: 44% according to ASTM D6866, trade name "BENEBiOL HS0850H", manufactured by Mitsubishi Chemical Corporation

[0179] NL1010DB: polycarbonate polyol having no ring structure, hydroxyl value: 113.5 mgKOH / g, biomass degree: 22% according to ASTM D6866, trade name "BENEBiOL NL1010DB", manufactured by Mitsubishi Chemical Corporation

[0180] UM-90(1 / 1): polycarbonate polyol having a carbon ring, hydroxyl value: 126.0 mgKOH / g, biomass degree: 0% according to ASTM D6866, trade name "ETERNACOLL UM-90(1 / 1)", manufactured by Ube Industries, Ltd.

[0181] UC-100: polycarbonate polyol having a carbon ring, hydroxyl value: 116.1 mgKOH / g, biomass degree: 0% according to ASTM D6866, trade name "ETERNACOLL UC-100", manufactured by Ube Industries, Ltd.

[0182] HEA: 2-hydroxyethyl acrylate, manufactured by FUJIFILM Wako Pure Chemical Corporation (reagent first class)

[0183] ARONIX M402: mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, trade name "ARONIX M402", manufactured by Toagosei Co., Ltd.

[0184] UA-306H: pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, manufactured by Kyoeisha Chemical Co., Ltd.

[0185] NEOSTANN U810: tin-based curing catalyst, manufactured by Nippon Soda Co., Ltd.

[0186] 2. Synthesis of urethane resin

[0187] <synthesis example 1>

[0188] To the dried flask, HS0850H 297.8 g, ethyl acetate 297.8 g, and NEOSTANN U8 100.12 g were added, and mixed with stirring at 45°C to make a uniform solution.

[0189] Next, 1,5-PDI 69.38 g as a polyisocyanate component, and PDI ureate 17.01 g were each added three times while warming to 70°C.

[0190] Next, after allowing the polyisocyanate component to react with HS0850H at 70°C for 1.5 hours, HEA 29.03 g, methyl ethyl ketone 65.60 g, and methylhydroquinone (Tokyo Chemical Industry Co., Inc., Reagent First Grade) 0.08 g were added, and a dry air was slowly bubbled while allowing to react for 1 hour.

[0191] Next, 1-methoxy-2-propanol 20.00 g was added, and after stirring at 70°C for 20 minutes, filtration was performed, whereby a urethane resin (solid content concentration: 50.0%, degree of biomass: 46.5%) was obtained.

[0192] Synthesis Examples 2 to 7

[0193] A urethane resin was obtained based on the same procedure as in Synthesis Example 1. However, the compounding prescription was changed according to Table 1.

[0194] 3. Preparation of a curable polyurethane resin composition

[0195] Examples 1 to 3, and Comparative Examples 1 to 4

[0196] A curable polyurethane resin composition (solid content concentration: 25 mass%) was prepared by mixing a urethane resin (solid content concentration: 50.0 mass%), dimethyl carbonate 10.45 g, and ethyl acetate 10.45 g, Irgacure 1173 (manufactured by BASF Japan Ltd.) 0.30 g as a photopolymerization initiator, according to the compounding prescription of Table 2 and Table 3, to make a uniform solution.

[0197] Examples 4 to 8, Examples 10 to 16, and Example 18

[0198] A curable polyurethane resin composition (solid content concentration: 25 mass%) was prepared by mixing a urethane resin (solid content concentration: 50.0 mass%), and a mixture of ARONIX M402 or UA-306H, and Irgacure 1173, dimethyl carbonate, and ethyl acetate (dimethyl carbonate: ethyl acetate = 1:1 (mass ratio)) at 3 parts by mass with respect to the total mass of the resin, according to the compounding prescription of Table 2 and Table 3, to make a uniform solution.

[0199] Example 9 and Example 17

[0200] A homogeneous curable urethane resin composition (25 mass% of solid content concentration) was prepared by mixing a urethane resin (50.0 mass% of solid content concentration), ARONIX M402 8.00 g, dimethyl carbonate 22.95 g, ethyl acetate 22.95 g, BYK333 (Shin-Etsu Chemical Co., Ltd.) 0.09 g as a leveling agent, and Irgacure 1173 0.54 g according to the compounding prescription of Table 2 and Table 3.

[0201] 4. Evaluation

[0202] <biomass degree>

[0203] The biomass degree was calculated based on the following formula (2).

[0204] The sum of (biomass degree x carbon content x amount of use) of each biomass raw material / the sum of (carbon content x amount of use) of all raw materials (2)

[0205] In the above formula (2), the biomass degree of each raw material was calculated based on American Test Material Standard (ASTM D6866).

[0206] The carbon content was calculated from the calculated value of the molecular formula for monomers and oligomers whose structures were known, and was calculated by elemental analysis for substances whose structures were unknown.

[0207] In addition, no organic solvent was included in all raw materials.

[0208] <evaluation of haze>

[0209] A curable urethane resin composition of each example and each comparative example was applied to one face in the thickness direction of a polycarbonate resin substrate (trade name "PC1600", 150 mm x 70 mm x thickness 2.0 mm, C.I. TAKIRON Corporation) as a coated body using an applicator 0.101 mm (type YA-4, Yoshimitsu Seiki Co., Ltd.), and was dried at 70°C for 2 minutes using a warm air drier, whereby solvent was distilled off, and a coating film was formed on one face in the thickness direction of the polycarbonate resin substrate.

[0210] Next, the polycarbonate resin substrate was passed once from inside the conveyer of the ultraviolet irradiation device, whereby ultraviolet rays were irradiated to the coating film (electrodeless H-bulb 240 W / cm 2Output 100%, lamp height 70 mm, conveyor speed 8.9 m / min, cumulative light amount 400 mJ / cm 2 The coating film was cured by using UV Power Puck II manufactured by Electronic Instrumentation & Technology, Inc.

[0211] Thus, the cured film was obtained, and thereby a laminate in which a cured film and a coated body are sequentially provided on one face in the thickness direction was obtained.

[0212] Next, the haze of the cured film immediately after curing was measured by using a haze meter (NDH-4000, manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Tables 2 and 3.

[0213] The cured film was subjected to abrasion resistance test. Specifically, a Shisutec abrasion tester (Shisutec Abrasion Tester II, manufactured by Yasuda Seiki Mfg. Co., Ltd.) was used, and the steel wool (BONSTAR #0000, manufactured by Nihon Steel Wool Co., Ltd.) was reciprocated 50 times with 500 g load applied. The haze was measured after the abrasion resistance test. The results are shown in Tables 2 and 3.

[0214] Note that, in the haze measurement, the test was performed twice, and the results were averaged.

[0215] 5. Discussion

[0216] <urethane resin of Synthesis Example 1 (polyisocyanate component: 1,5-PDI and PDI urethane, hydroxyl component: polyol containing a heterocycle)>

[0217] The urethane resin of Synthesis Example 1 was used in Example 1, Examples 4 to 9.

[0218] Example 1 does not contain a polyfunctional (meth)acrylate, and Examples 4 to 9 contain a polyfunctional (meth)acrylate.

[0219] In the case of Example 1, the haze of the cured film immediately after curing was less than 0.5% in the haze test. Thus, it was found that the turbidity of the cured film could be suppressed.

[0220] In addition, in the case of Examples 4 to 9, the haze of the cured film immediately after curing was less than 0.5% in the haze test. Thus, it was found that even if the curable polyurethane resin composition contains a polyfunctional (meth)acrylate, the turbidity of the cured film could be suppressed.

[0221] <urethane resin of synthetic example 2 (polyisocyanate component: 1,5-PDI, hydroxyl component: heterocycle-containing polyol)>

[0222] Example 2, Examples 10 to 17 used the urethane resin of synthetic example 2.

[0223] The curable polyurethane resin composition of Example 2 does not contain a polyfunctional (meth)acrylate, and Examples 10 to 17 contain a polyfunctional (meth)acrylate.

[0224] It was found that Example 2, like the above-described Example 1, was able to suppress turbidity of the cured film.

[0225] It was found that Examples 10 to 17, like the above-described Examples 4 to 9, were able to suppress turbidity of the cured film even if the curable polyurethane resin composition contained a polyfunctional (meth)acrylate.

[0226] <urethane resin of synthetic example 6 (polyisocyanate component: 1,6-HDI, hydroxyl component: heterocycle-containing polyol)>

[0227] Example 3 and Example 18 used the urethane resin of synthetic example 6.

[0228] The curable polyurethane resin composition of Example 3 does not contain a polyfunctional (meth)acrylate, and Example 18 contains a polyfunctional (meth)acrylate.

[0229] It was found that Example 3, like the above-described Example 1, was able to suppress turbidity of the cured film.

[0230] It was found that Example 18, like the above-described Examples 4 to 9, was able to suppress turbidity of the cured film even if the curable polyurethane resin composition contained a polyfunctional (meth)acrylate.

[0231] <urethane resin of synthetic example 3 (polyisocyanate component: 1,5-PDI, hydroxyl component: polycarbonate polyol having no ring structure)>

[0232] Comparative Example 1, Comparative Example 5, and Comparative Example 6 used the urethane resin of synthetic example 3.

[0233] The curable polyurethane resin composition of Comparative Example 1 does not contain a polyfunctional (meth)acrylate, and Comparative Examples 5 and 6 contain a polyfunctional (meth)acrylate.

[0234] In the case of Comparative Example 1, the haze of the cured film immediately after curing was greater than 0.5% in the haze test. It was found that turbidity of the cured film could not be suppressed.

[0235] In addition, in Comparative Example 5 and Comparative Example 6, the haze of the cured film immediately after curing was greater than 0.5%. Thus, even if the curable polyurethane resin composition contains a multifunctional (meth)acrylate, the haze of the cured film cannot be inhibited.

[0236] <urethane resin of Synthesis Example 4 (polyisocyanate component: 1,5-PDI, hydroxyl component: polycarbonate polyol having a carbocyclic ring)>

[0237] Comparative Example 2, Comparative Example 7, and Comparative Example 8 used the urethane resin of Synthesis Example 4.

[0238] The curable polyurethane resin composition of Comparative Example 2 does not contain a multifunctional (meth)acrylate, and Comparative Examples 7 and 8 contain a multifunctional (meth)acrylate.

[0239] It was found that Comparative Example 2, like Comparative Example 1 described above, could not inhibit the haze of the cured film.

[0240] In addition, it was found that Comparative Examples 7 and 8, like Comparative Examples 5 and 6 described above, could not inhibit the haze of the cured film even if the curable polyurethane resin composition contained a multifunctional (meth)acrylate.

[0241] <urethane resin of Synthesis Example 5 (polyisocyanate component: 1,5-PDI, hydroxyl component: polycarbonate polyol having a carbocyclic ring)

[0242] Comparative Example 3, Comparative Example 9, and Comparative Example 10 used the urethane resin of Synthesis Example 5.

[0243] The curable polyurethane resin composition of Comparative Example 3 does not contain a multifunctional (meth)acrylate, and Comparative Examples 9 and 10 contain a multifunctional (meth)acrylate.

[0244] In the haze test, the haze of the cured film immediately after curing was less than 0.5% in Comparative Example 3, whereas the haze of the cured film immediately after curing was greater than 0.5% in Comparative Examples 9 and 10. Thus, if a multifunctional (meth)acrylate is incorporated in the curable polyurethane resin composition of Comparative Example 3, the haze of the cured film cannot be inhibited.

[0245] <urethane resin of Synthesis Example 7 (polyisocyanate component: 1,6-HDI, hydroxyl component: polycarbonate polyol having a carbocyclic ring)

[0246] Comparative Example 4, Comparative Example 11, and Comparative Example 12 used the urethane resin of Synthesis Example 7.

[0247] The curable polyurethane resin composition of Comparative Example 4 does not contain a polyfunctional (meth)acrylate, and Comparative Examples 11 and 12 contain a polyfunctional (meth)acrylate.

[0248] As is apparent from Comparative Example 4, Comparative Example 11, and Comparative Example 12, as well as Comparative Example 3, Comparative Example 9, and Comparative Example 10 described above, if a polyfunctional (meth)acrylate is incorporated in the curable polyurethane resin composition of Comparative Example 4, the haze of the cured film cannot be inhibited.

[0249] <biomass degree>

[0250] The polyols from plants (polyols from plants containing a heterocycle) were used in Examples 1 to 18.

[0251] Further, the biomass degree of Examples 1 to 18 was 10 or more. Therefore, it is apparent that the environmental load can be reduced. In particular, in the case of Example 3 and Example 18, since 1,5-PDI from plants is not contained and 1,6-HDI is contained, the hydroxyl component contains a polyol from plants (a polyol from plants containing a heterocycle), and thus the biomass degree can be increased.

[0252] [Table 1]

[0253]

[0254] [Table 2]

[0255]

[0256] [Table 3]

[0257]

[0258] Note that the above-described application is provided as an example of an embodiment of the present application, but it is merely an example and is not to be construed as limiting. Modifications of the present application apparent to those skilled in the art are included in the appended claims.

[0259] Industrial applicability

[0260] The curable polyurethane resin composition, the cured product, and the laminate of the present application can be suitably used in various industrial products such as plastic films, plastic sheets, plastic foams, spectacle lenses, spectacle frames, fibers, artificial leather, synthetic leather, metals, wood, and the like.

[0261] Explanation of reference signs

[0262] 1 Laminate

[0263] 2 Coated body

[0264] 3 Cured film

Claims

1. A curable polyurethane resin composition comprising a reaction product of a polyisocyanate component and a hydroxyl component, The polyisocyanate component includes aliphatic diisocyanates and / or their derivatives. The hydroxyl component contains only: Heterocyclic polyols derived from plants, wherein the polyols contain heterocyclic structures and are derived from plants; and A hydroxyl-containing unsaturated compound, wherein the hydroxyl-containing unsaturated compound contains an olefinic unsaturated group and a hydroxyl group. The reaction product is the reaction product of the isocyanate-terminated prepolymer and the hydroxyl-containing unsaturated compound. The isocyanate group equivalent ratio of the isocyanate group to the hydroxyl group of the hydroxyl-containing unsaturated compound in the isocyanate-terminated prepolymer is 0.7 to 1.

3. The isocyanate-terminated prepolymer is a reaction product of the polyisocyanate component and the heterocyclic polyol derived from plants. The isocyanate group of the polyisocyanate component has an equivalent ratio of 1.5 to 20 relative to the hydroxyl group of the heterocyclic plant-derived polyol. The aliphatic diisocyanate is pentamethylene diisocyanate and / or hexamethylene diisocyanate. The heterocyclic polyol derived from plants is isosorbide-modified polycarbonate polyol. The hydroxyl-containing unsaturated compound is a monohydroxy mono(meth)acrylate.

2. The curable polyurethane resin composition according to claim 1, wherein, The aliphatic diisocyanate comprises 1,5-pentanediisocyanate derived from plants.

3. The curable polyurethane resin composition of claim 1, further comprising a polyfunctional (meth)acrylate having three or more olefinically unsaturated groups. The product contains 30 or more parts by mass of the polyfunctional (meth)acrylate relative to 100 parts by mass of the reaction product.

4. The cured product of the curable polyurethane resin composition according to claim 1.

5. The cured product as described in claim 4, wherein the haze is less than 0.5%.

6. A laminate having, in the thickness direction, a coated body and a cured film formed from the cured material of claim 4.

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