WO2018173637A1 - 水系ポリウレタン樹脂組成物 - Google Patents
水系ポリウレタン樹脂組成物 Download PDFInfo
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- WO2018173637A1 WO2018173637A1 PCT/JP2018/006885 JP2018006885W WO2018173637A1 WO 2018173637 A1 WO2018173637 A1 WO 2018173637A1 JP 2018006885 W JP2018006885 W JP 2018006885W WO 2018173637 A1 WO2018173637 A1 WO 2018173637A1
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- urethane prepolymer
- resin composition
- polyurethane resin
- water
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8166—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with unsaturated monofunctional alcohols or amines
Definitions
- the present invention relates to an aqueous polyurethane resin composition, and more specifically, a urethane prepolymer composition comprising a urethane prepolymer obtained by reacting a polyisocyanate component, a polyol component and an anionic group introducing agent, and a cationic curable substance.
- a urethane prepolymer composition comprising a urethane prepolymer obtained by reacting a polyisocyanate component, a polyol component and an anionic group introducing agent, and a cationic curable substance.
- the water-based polyurethane resin composition is useful because it can be used for various applications such as paints, adhesives, fiber sizing agents, leather, substrate impregnation, and backing.
- optical films are used for liquid crystal displays used in televisions and personal computers, for example, polarizer protective films, retardation films, viewing angle protective films, and the like. These optical films are composed of a base material layer made of polyester resin, polycarbonate resin or the like, and a layer made of energy ray curable resin cured by ultraviolet rays or the like. Specifically, optical films described in Patent Documents 1 to 6 are known.
- Patent Document 1 describes an easily adhesive polyester film for optics using a water-based polyurethane resin composition as an adhesive layer.
- the water-based polyurethane resin composition described in this document cannot exhibit sufficient performance with respect to adhesion with a layer made of an energy ray curable resin cured by ultraviolet rays or the like.
- Patent Document 2 describes a polarizing plate in which a cycloolefin resin film is laminated on a polarizing film made of a polyvinyl alcohol resin via an adhesive layer.
- blending an oxetane compound and an epoxy compound is used for the adhesive bond layer.
- an oxetane compound or an epoxy compound is simply added to an aqueous urethane composition, a product having sufficient storage stability cannot be obtained, and the aqueous urethane composition is cured with a base material layer such as a polyester resin and ultraviolet rays.
- a base material layer such as a polyester resin and ultraviolet rays.
- Citations 3, 4, 5 and 6 describe combinations of water-based urethane resins and epoxy compounds such as ⁇ -methylglycidyl compounds, but the aqueous resins described in these documents include polyester resins and the like. When used in a system composed of a base material layer and an energy ray curable resin layer cured by ultraviolet rays or the like, only those having poor adhesion can be obtained.
- the present inventors are particularly useful as an adhesive for an optical film obtained by applying a layer made of an energy ray curable resin that is cured by ultraviolet rays or the like to a substrate made of PET, PC, or the like. Efforts were made to obtain an aqueous polyurethane resin composition.
- the present invention relates to a urethane prepolymer comprising (A) a urethane prepolymer obtained by reacting (a) a polyisocyanate component, (b) a polyol component, and (c) an anionic group introducing agent, and (B) a cationic curable substance.
- An aqueous polyurethane resin obtained by dispersing a polymer composition in water to obtain an aqueous dispersion, and reacting the obtained (A) urethane prepolymer in the aqueous dispersion with (C) a blocking agent and / or a chain extender.
- a composition is provided.
- a urethane prepolymer obtained by reacting (a) a polyisocyanate component, (b) a polyol component, and (c) an anionic group introducing agent is used.
- a polyisocyanate component which is the component (a) used in the present invention a known polyisocyanate component can be used without particular limitation.
- diisocyanate examples include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate.
- Aromatic diisocyanates such as dianisidine diisocyanate and tetramethylxylylene diisocyanate; cycloaliphatic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans-1,4-cyclohexyl diisocyanate, norbornene diisocyanate; 1,6 Hexamethylene diisocyanate, 2,2,4 and / or (2,4,4) -trimethylhexamethylene diisocyanate, lysine diiso Aliphatic diisocyanates such as cyanate are mentioned, and among these diisocyanates, alicyclic diisocyanates are preferred because they are excellent in the hydrolyzability of the resulting polyurethane molecules and the coating films obtained therefrom.
- Isophorone diisocyanate dicyclohexylmethane- More preferred is 4,4′-diisocyanate.
- These diisocyanates can be used alone or in combination of two or more.
- the above diisocyanates can be used in the form of modified products such as carbodiimide modification, isocyanurate modification, biuret modification, etc., and can be used in the form of blocked isocyanates blocked with various blocking agents.
- the polyisocyanate component which is (a) component used by this invention may contain the polyisocyanate which has three or more isocyanate groups in 1 molecule.
- polyisocyanates having three or more isocyanate groups in one molecule include, for example, isocyanurate trimers, burette trimers, trimethylolpropane adducts of the above-mentioned diisocyanates; triphenylmethane triisocyanate, 1- Examples thereof include methylbenzole-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, etc.
- isocyanate compounds may be used in the form of carbodiimide modification, isocyanurate modification, biuret modification, etc., and various blocking agents. Can be used in the form of blocked isocyanates blocked by These can be used alone or in combination of two or more.
- the polyisocyanate component which is the component (a) if the diisocyanate content is less than 50% by mass, the storage stability may be lowered, so 50% by mass or more is preferable, and 70% by mass or more is more preferable. preferable.
- the polyisocyanate component as component (a) used in the present invention preferably contains an alicyclic diisocyanate. Since the polyisocyanate component as the component (a) contains an alicyclic diisocyanate, performances such as solvent resistance and alkali resistance of the coating film are improved.
- low molecular polyol examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2-butyl-2-ethyl-1,3-propane.
- the polycarbonate polyol is obtained by reacting a carbonate ester and / or phosgene with the low molecular polyol exemplified above.
- the carbonate ester include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, diphenyl carbonate, dinaphthyl carbonate, and phenyl naphthyl carbonate.
- polyester polyol direct esterification of the low molecular polyol exemplified above with a polyvalent carboxylic acid having an amount less than the stoichiometric amount of the polyol or an ester-forming derivative such as an ester, an anhydride or a halide thereof. What is obtained by reaction and / or transesterification is mentioned.
- polyvalent carboxylic acid or an ester-forming derivative thereof examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, Aliphatic dicarboxylic acids such as dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid; 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2- Cyclohexanedicarboxylic
- polyether polyols examples include water, ethylene oxide and / or propylene oxide adducts of the above low molecular polyols, and polytetramethylene glycol.
- silicone polyol examples include silicone oils having a hydroxyl group at the terminal having a siloxane bond in the molecule.
- the polyol component which is the component (b) used in the present invention preferably contains a polycarbonate diol, and among the polycarbonate diols, those having an average molecular weight of 500 to 5000 are preferred. If the average molecular weight is less than 500, sufficient coating film adhesion to the substrate may not be obtained, and if it exceeds 5000, the storage stability and impact resistance of the product may be reduced.
- the content of the polycarbonate diol in the polyol component which is the component (b) is preferably 50% by mass or more, more preferably 70% by mass in the polyol component which is the component (b).
- the polyol component as the component (b) is intended to improve durability by using a small amount of polyfunctional polyol such as trimethylolpropane (less than 10% by mass in the polyol component as the component (b)). Can do.
- a urethane prepolymer is produced by reacting a polyisocyanate, a polyol, and an anionic group introducing agent (as an anionic group-containing polyol), the total isocyanate group equivalent (NCO) of the polyisocyanate group, the polyol and the anion
- NCO isocyanate group equivalent
- the terminal structure of the urethane prepolymer to be obtained varies depending on the ratio to the total hydroxyl equivalent (OH) of the functional group introducing agent. Since the urethane prepolymer used in the present invention is preferably an isocyanate group at the end, it is preferable to adjust NCO / OH to be larger than 1.0, more preferably 1.1 to 2.5. And more preferably in the range of 1.2 to 2.0.
- NCO / OH When NCO / OH is 1.0 or less, particularly less than 1.1, the obtained urethane prepolymer has a high molecular weight and water dispersibility is lowered, and it reacts with a blocking agent and / or a chain extender. Therefore, there is a possibility that the NCO group for the purpose is reduced and the storage stability of the resulting aqueous polyurethane resin composition is adversely affected.
- NCO / OH is greater than 2.0, the isocyanate group and water react when the obtained prepolymer is dispersed in water to generate carbon dioxide, which causes problems during production such as rapid foaming. There is a fear, and even when an aqueous polyurethane resin composition is used, it is not preferable because there is a risk of performance deterioration such as adhesion to the substrate.
- the use ratio (mass ratio) of the polyol (b) and the anionic group-introducing agent (c) is the former / the latter in the range of 99.9 / 0.1 to 70/30. It can be selected appropriately.
- the acid value of the urethane prepolymer as the component (A) has an influence on the blocking performance.
- the acid value of the urethane prepolymer as component (A) is preferably set in the range of 20 to 90 mgKOH / g, more preferably 30 to 80 mgKOH / g, and particularly preferably 40 to 70 mgKOH / g.
- the amount of the anionic group introducing agent as the component (c) is adjusted so as to be in such a range.
- the acid value of the urethane prepolymer which is the above-mentioned component (A) is a theoretical value obtained from the blending amount of the reaction component of the urethane prepolymer which is the component (A).
- the measurement value of the acid value of the urethane prepolymer as the component (A) obtained varies from the above theoretical value. To do. There is the following relationship among the above-described theoretical values, measured values, and theoretical values.
- Acid value (theoretical value) acid value (measured value) ⁇ [(a) + (b) + (c) + solvent: total mass] / [(a) + (b) + (c): total mass]
- a catalyst can be used as necessary.
- a catalyst include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N “, N”.
- These catalysts can be used independently and can use 2 or more types together.
- the amount of these catalysts used is not limited, but is preferably 0.001 to 1% by mass, more preferably 0.01 to 0%, based on the total amount of component (a), component (b) and component (c). .1% by mass.
- a crosslinked structure can be introduced using a crosslinking agent.
- a crosslinking agent the crosslinking agent normally used at the time of manufacture of a urethane prepolymer can be used.
- cross-linking agents include melamine, monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, methylated methylol melamine, butylated methylol melamine, melamine resin and the like. Can be used.
- crosslinking agents melamine which is excellent in compatibility with polyurethane and inexpensive is preferable.
- the amount used in the case of using these crosslinking agents is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyol (a). is there.
- the urethane prepolymer which is the component (A) used in the present invention is an optional component and a polyisocyanate which is the component (a), a polyol which is the component (b) and an anionic group introducing agent which is the component (c).
- the catalyst and / or the crosslinking agent can be obtained by heating reaction in the presence of an arbitrary inert solvent.
- an arbitrary inert solvent There is no restriction
- the inert solvent used here include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone and the like having a high affinity for water.
- the amount of the solvent used is not particularly limited, but is preferably 3 to 200 parts by mass with respect to 100 parts by mass of the total amount of the raw material for the urethane prepolymer as component (A).
- the cationic curable substance which is the component (B) used in the present invention is a compound that is polymerized or undergoes a crosslinking reaction by a cationic polymerization initiator activated by irradiation with energy rays such as ultraviolet rays or heating.
- a cationic polymerization initiator activated by irradiation with energy rays such as ultraviolet rays or heating.
- Examples of the cationic curable substance as component (B) include oxetane compounds, epoxy compounds, and the like, and since they have excellent storage stability when used as water-based polyurethane resin compositions, oxetane compounds and ⁇ -alkylglycidyl compounds. Is a more preferred compound. These can be used alone or in combination of two or more.
- oxetane compound examples include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and 3-ethyl-3.
- Monofunctional oxetane compounds such as-(phenoxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3-ethyl-3-[(3-triethoxysilylpropoxy) methyl] oxetane, oxetanylsilsesquioxane; 1,4-bis [ ⁇ (3-ethyl-3-oxetanyl) methoxy ⁇ methyl] benzene, 4,4′-bis [ ⁇ (3-ethyl-3-oxetanyl) methoxy ⁇ methyl] biphenyl, bis [(3- Ethyl-3-oxetanyl) methyl] ether, 1,2-bis [(3-ethyl-3- Xetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, 1,4-bis (3-
- oxetane compound a commercially available product having an oxetane compound as a main component can be used.
- Examples of the epoxy compound include aliphatic epoxy compounds, aromatic epoxy compounds, and alicyclic epoxy compounds.
- Examples of the aliphatic epoxy compound include monofunctional epoxy compounds such as glycidyl etherified products of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, polyglycidyl etherified products of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and fats. And polyfunctional epoxy compounds such as polyglycidyl esters of group long-chain polybasic acids.
- Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, triglycidyl ether of glycerin.
- Polyglycols such as triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, dicyclopentadiene dimethanol diglycidyl ether Glycidyl ether, also propylene glycol, trimethylolpropane, glycerin, Examples thereof include polyglycidyl etherified products of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as hydrogenated bisphenol A, and diglycidyl esters of aliphatic long-chain dibasic acids.
- aliphatic epoxy compound commercially available products can be used.
- the aromatic epoxy compound refers to an epoxy compound containing an aromatic ring
- specific examples of the aromatic epoxy compound include a polyhydric phenol having at least one aromatic ring such as phenol, cresol, butylphenol, or the like.
- Mono / polyglycidyl etherified products of aromatic compounds having a functional hydroxyl group aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol and phenyldibutanol
- aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol and phenyldibutanol
- Glycidyl esters of polybasic aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, glycidyl esters of benzoic acid, epoxides of styrene oxide or divinylbenzene It is done.
- the aromatic epoxy compound commercially available products can be used.
- Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, ONCOAT EX-1020, ONCOAT EX-1030, ONCOAT EX-1040, ONCOAT EX-1050, ONCOAT EX-1051, ONCOAT EX-1010, ONCOAT EX-1011, ONCOAT 1012 Nagase ChemteX Corporation Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical); HP4032, HP4032D, HP4700 (DIC); ESN-475V (Toto Kasei) YX8 00 (Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (NOF Corporation); Epicron N-665, Epicron HP-7200 (DIC Corporation); EO
- the alicyclic epoxy compound refers to a compound in which an oxirane ring is directly bonded to a saturated ring without a spacer, and specific examples of the alicyclic epoxy compound include at least one alicyclic ring. Examples thereof include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by epoxidizing a polyglycidyl etherified polyhydric alcohol or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent.
- 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4 -Epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5 -Methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxy Cyclohexane), propane-2,2-diyl-bis (3,
- alicyclic epoxy compound Commercially available products can be used as the alicyclic epoxy compound, and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 (manufactured by Daicel).
- the ⁇ -alkylglycidyl compound mentioned as the preferred epoxy compound has a structure obtained by condensing ⁇ -alkylephydrin and a hydroxy compound.
- the ⁇ -alkyl glycidyl compound used in the present invention is not limited by its production method.
- ⁇ -alkylephahydrin examples include, for example, ⁇ -methylepichlorohydrin, ⁇ -methylepibromohydrin, ⁇ -methylepifluorohydrin, ⁇ -ethylepichlorohydrin, ⁇ -ethylepibromohydrin.
- Phosphorus ⁇ -ethyl epifluorohydrin, ⁇ -propyl epichlorohydrin, ⁇ -propyl epibromohydrin, ⁇ -propyl epifluorohydrin, ⁇ -butyl epichlorohydrin, ⁇ -butyl epibromohydrin, and ⁇ -butyl epifluorohydrin.
- hydroxy compound examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, hydroquinone, resorcin, pyrocatechol, phloroglucinol, dihydroxynaphthalene.
- Biphenol methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxydic Milbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxy) Phenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, dihydroxynaphthalene, phenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol, dicyclo Pentadiene / phenol polyadduct, ethylene glycol, propylene glycol, butylene glycol, hexanediol, poly
- adhesion to an energy ray-curable resin layer cured by ultraviolet rays or the like by using a compound having two or more ⁇ -methylglycidyl groups such as bisphenol A di ⁇ -methylglycidyl ether. It is preferable because a water-based polyurethane resin composition having excellent resistance can be obtained.
- a urethane prepolymer composition containing a urethane prepolymer as component (A) and a cationic curable substance as component (B) is prepared.
- the use ratio (mass ratio) of the urethane prepolymer as the component (A) and the cationic curable material as the component (B) is the former: the latter, preferably 100: 1-50.
- the use ratio of the component (B) is less than 1, use effects such as adhesion may not be obtained, and when it exceeds 50, storage stability may be deteriorated.
- a well-known method is employable.
- a urethane prepolymer composition containing the urethane prepolymer as the component (A) and the cationic curable material as the component (B) is dispersed in water to obtain water dispersion.
- the method for dispersing the urethane prepolymer composition in water is not particularly limited. For example, a prepolymer mixing method and a phase inversion method can be used.
- the prepolymer mixing method is a method in which a prepolymer composition obtained by mixing the components (A) and (B) is dispersed in water.
- the anionic group neutralizing agent and / or the emulsifier can be added to the prepolymer composition, and can be added to water.
- the phase inversion method is a method in which water is added and dispersed in a prepolymer composition obtained by mixing the components (A) and (B).
- the anionic group neutralizing agent and / or the emulsifier can be added to the prepolymer composition, and can be added to water.
- the anionic group neutralizing agent is, for example, a basic compound that reacts with an anionic group to form a hydrophilic salt.
- trialkylamines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dipropylethanolamine, 1-dimethylamino-2-methyl-2 -Tertiary amine compounds such as N, N-dialkylalkanolamines such as propanol and trialkanolamines such as triethanolamine; ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. It is done.
- aqueous polyurethane resin composition of the present invention can be used alone or in combination of two or more.
- a highly volatile anionic group neutralizing agent that is easily dissociated by heat.
- trimethylamine and triethylamine are preferable.
- the amount of the anionic group neutralizing agent used is from the viewpoint of storage stability of the water-based polyurethane resin composition obtained by the present invention, and mechanical properties such as strength of the product obtained by using the same and performance such as water resistance.
- the amount is preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents, relative to 1 equivalent of the anionic group.
- a known surfactant can be used as the emulsifier.
- known general anionic surfactants, nonionic surfactants, cationic surfactants, double-sided surfactants, polymer surfactants, reactive surfactants, and the like can be used.
- anionic surfactant examples include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinolate; alkali metal salt of sulfonated paraffin, sulfone Alkyl sulfonates such as ammonium salts of chlorinated paraffins; fatty acid salts such as sodium laurate, triethanolamine oleate, and triethanolamine abiates; alkyl aryl sulfonates such as sodium benzene sulfonate and alkali metal sulfates of alkylphenol hydroxyethylene; high alkyl naphthalene sulfones Acid salt; naphthalenesulfonic acid formalin condensate; dialkyl sulfone Polyoxyethylene alkyl sulfate
- nonionic surfactant examples include fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate; polyoxyethylene glycol fatty acid esters; polyglycerin fatty acid esters; alcohol having 1 to 18 carbon atoms.
- fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate
- polyoxyethylene glycol fatty acid esters such as sorbitan monolaurate and sorbitan monooleate
- polyoxyethylene glycol fatty acid esters such as sorbitan monolaurate and sorbitan monooleate
- polyoxyethylene glycol fatty acid esters such as sorbitan monolaurate and sorbitan monooleate
- polyoxyethylene glycol fatty acid esters such as sorbitan monolaurate and sorbitan monooleate
- polyoxyethylene glycol fatty acid esters such as sorbitan monolaurate and sorb
- Examples of the alcohol having 1 to 18 carbon atoms constituting the nonionic surfactant include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tertiary butanol, amyl alcohol, isoamyl alcohol, and tertiary amyl alcohol.
- Hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, etc., and alkylphenols include phenol, methylphenol, 2,4-ditertiarybutylphenol, 3,5-ditertiary alcohol.
- alkylene glycol examples include ethylene glycol, 1,2-propanediol, 1,3- Propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-methyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl 1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol and the like.
- the alkylene diamine the alcoholic hydroxyl group of the above alkylene glycol is substituted with an amino group. What has been done.
- the ethylene oxide adduct and the propylene oxide adduct may be a random adduct or a block adduct.
- Examples of the cationic surfactant include primary to tertiary amine salts; alkylpyridinium salts such as pyridinium salts such as alkylpyridinium bromides; imidazolinium salts such as imidazolinium laurate; lauryltrimethylammonium chloride, Examples thereof include quaternary ammonium salts such as stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, and alkyl quaternary ammonium salts.
- amphoteric surfactant examples include coconut oil fatty acid amidopropyldimethylacetate betaine, lauryldimethylamino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, laurylhydroxysulfobetaine, lauroylamidoethyl.
- Betaine-type amphoteric surfactants such as hydroxyethylcarboxymethylbetaine and metal salts of hydroxypropyl phosphate
- amino acid-type amphoteric surfactants such as metal salts of ⁇ -laurylaminopropionic acid
- sulfate-type amphoteric surfactants sulfonic acids Type amphoteric surfactants and the like.
- the amount of the emulsifier is not particularly limited, but from the viewpoint of performance such as water resistance of the cured product of the product obtained from the aqueous polyurethane resin composition of the present invention, the total amount of solid content of the urethane prepolymer composition is 100 parts by mass. Is preferably 0 to 30 parts by mass, and more preferably 0 to 20 parts by mass.
- the water-based polyurethane resin composition of the present invention is obtained by adding a blocking agent and / or a chain extender as component (C) as a solution to a water-dispersed urethane prepolymer composition as necessary.
- the urethane prepolymer which is the component (A) contained in the composition is obtained by blocking and / or chain extension in water.
- Examples of the blocking agent used in the present invention include alcohols such as methanol and ethanol; dialkylamines such as diethylamine, dimethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, didodecylamine and distearylamine. Diarylamines such as diphenylamine; secondary amino group-containing heterocyclic compounds such as morpholine, piperidine, pyrrole, pyrrolidine, pyrazole and imidazole. Among these, a water-soluble secondary amine, particularly diethylamine is preferable.
- chain extender used in the present invention examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl- 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5 -Pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1 , 8-octanediol, 2-methyl-1,8-octanediol, 1,9-non
- the usage-amount of blocking agent is contained in the blocking agent with respect to the isocyanate group equivalent contained in the urethane prepolymer which is the (A) component before blocking. It is preferable to set the amount so that the ratio of isocyanate reactive group equivalents is in the range of 0.1 to 1.0.
- the amount of the chain extender used is the chain extension relative to the isocyanate group equivalent contained in the urethane prepolymer as the component (A) before chain extension. It is preferable to set the amount so that the ratio of equivalents of isocyanate reactive groups contained in the agent is in the range of 0.1 to 1.0.
- the amount of the blocking agent and the chain extender used is the isocyanate contained in the urethane prepolymer which is the component (A) before the blocking and chain extension.
- the ratio of the isocyanate reactive group equivalent contained in the blocking agent and the chain extender to the group equivalent is preferably set to an amount in the range of 0.1 to 1.0.
- the aqueous polyurethane resin composition of the present invention contains a specific polyurethane as a main component.
- the polyurethane contained in the aqueous polyurethane resin composition of the present invention comprises (A) a urethane prepolymer obtained by reacting (a) a polyisocyanate component, (b) a polyol component, and (c) an anionic group introducing agent, and (B ) It is obtained by reacting a cationic curable substance with (C) a blocking agent and / or a chain extender in the presence of water. Therefore, the repeating unit of the polyurethane contained in the water-based polyurethane resin composition of the present invention is not uniform, and its structure and repetition are rich in variety.
- the structure of the polyurethane contained in the water-based polyurethane resin composition of the present invention is very complicated. For this reason, the present situation is that it is impossible to uniformly represent the structure of the polyurethane included in the present invention by a certain general formula, and this is common technical knowledge of those skilled in the art. And if the structure is not specified, the characteristics of the substance determined according to it cannot be easily understood, so it cannot be expressed by characteristics. Therefore, in the present invention, the invention “aqueous polyurethane resin composition” characterized by containing such polyurethane is reacted with “(a) polyisocyanate component, (b) polyol component and (c) anionic group introducing agent”.
- a urethane prepolymer composition containing (A) a urethane prepolymer and (B) a cationic curable material was prepared, and then the urethane prepolymer composition was dispersed in water to obtain an aqueous dispersion.
- the water-based polyurethane resin composition of the present invention its solid content [1 g of water-based polyurethane resin composition was weighed into an aluminum cup and calculated from the weight before and after drying for 1 hour in a thermostatic bath at 150 ° C. ] Is not particularly limited, and any value can be selected.
- the solid content of the aqueous polyurethane resin composition of the present invention is preferably 10 to 70% by mass because dispersibility and paintability are good, and more preferably 20 to 60% by mass.
- the weight average molecular weight of the polyurethane dispersed in the water-based polyurethane resin composition of the present invention is not particularly limited, and the range that gives dispersibility as a water-based paint and a good coating film can be selected.
- the weight average molecular weight is preferably from 5,000 to 2,000,000, more preferably from 10,000 to 100,000.
- the hydroxyl value is not particularly limited. This value is usually 1 to 100 in terms of KOH consumption (mg) per gram of resin.
- the state of the aqueous polyurethane resin composition of the present invention is an emulsion, suspension, colloidal dispersion, aqueous solution, or the like.
- particle size measured using a dynamic scattering device
- colloidal dispersions in which particles are dispersed in water, but a good dispersion state can be maintained, so 1 ⁇ m or less Is preferable, 500 nm or less is more preferable, and 100 nm or less is particularly preferable.
- aqueous polyurethane resin composition of the present invention various commonly used additives can be used as necessary.
- the additive include a hindered amine light stabilizer, an ultraviolet absorber, a phosphorus antioxidant, a phenol antioxidant, a sulfur antioxidant, a pigment, a dye, a film-forming aid, a curing agent, and a crosslinking agent.
- Silane coupling agents Silane coupling agents, antiblocking agents, viscosity modifiers, leveling agents, antifoaming agents, antigelling agents, dispersion stabilizers, radical scavengers, heat resistance imparting agents, inorganic and organic fillers, plasticizers, lubricants, Examples thereof include an antistatic agent, a reinforcing agent, a catalyst, a thixotropic agent, an antibacterial agent, an antifungal agent, an anticorrosive agent, and a cationic polymerization initiator.
- hindered amine light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 1,2,2,6,6-pentamethyl-4-piperidylmethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidylmethyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4 -Piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)- , 2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-
- ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone).
- 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5 -Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5- Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-th Octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acroyl) Oxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-
- Examples of the phosphorus-based antioxidant include triphenyl phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tris (2,5-ditertiarybutylphenyl) phosphite, and tris (nonylphenyl).
- Phosphite tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octyl phosphite , Diphenyldecyl phosphite, diphenyloctyl phosphite, bis (nonylphenyl) pentaerythritol phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite Ite, dibutyl acid phosphite, dilauryl acid phosphite, tril
- phenolic antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-bis (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3 3-bis (4-hydroxy-3-tert-but
- sulfur-based antioxidant examples include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate).
- dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid
- polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate).
- the amount used can be appropriately selected.
- a weather resistance-imparting agent such as the above-mentioned hindered amine light stabilizer, ultraviolet absorber, phosphorus antioxidant, phenol antioxidant, or sulfur antioxidant
- the amount used is the amount of the present invention. If the amount is less than 0.001 part by mass relative to 100 parts by mass of the solid content of the water-based polyurethane resin composition, a sufficient addition effect may not be obtained. Since there is a possibility, 0.001-10 mass parts is preferable, and 0.01-5 mass parts is more preferable.
- Examples of methods for adding these various additives include a method of adding to the polyol component, a method of adding to the prepolymer, a method of adding to the aqueous phase during water dispersion, and a method of adding after water dispersion. You can choose the method.
- the aqueous polyurethane resin composition of the present invention can be used for various applications such as paints, adhesives, fiber sizing agents, leather, substrate impregnation, and backing.
- the water-based polyurethane resin composition of the present invention is particularly suitable for use in a cationic curing composite system by energy such as heat or ultraviolet rays, for example, an optical film using an energy ray curable resin cured by ultraviolet rays or the like. It can be used suitably for a use.
- an optically anisotropic layer containing a liquid crystalline compound is laminated on one side of a support, and a hard coat layer is laminated on the opposite side. It is a laminated body.
- Such an optical film is, for example, a polarizer protective film, a retardation film, a viewing angle compensation film, a light diffusion film, a reflective film, an antireflection film, an antiglare film, a conductive film for a touch panel, a prism sheet, and the like.
- the water-based urethane composition of the present invention can be suitably used for a polarizer protective film, a retardation film, and a viewing angle protective film.
- these optical films are prepared by attaching a coating layer obtained from a photocurable resin monomer and a polymerization initiator to a sheet-like plastic substrate.
- the water-based polyurethane resin composition of the present invention is suitable as a binder, that is, an easy adhesion layer, through a plastic substrate and a layer obtained from a photocurable resin and a photopolymerization initiator.
- plastic substrate examples include polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane- Polyester resins such as 4,4'-dicarboxylate and polybutylene terephthalate; Silicon resins; Acrylic resins such as polymethyl methacrylate and polyacrylate; Epoxy resins; Fluorine resins, polystyrene, polyvinyl chloride, polyvinyl fluoride Vinyl compounds such as polycarbonate, (PC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), cycloolefin polymer (COP); triacetyl cellulose (TAC), Cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose and nitrocellulose
- examples of the energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies, and the like, and ultraviolet rays are most economically preferable.
- examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
- the method for applying the aqueous polyurethane resin composition of the present invention to a plastic substrate is not particularly limited.
- coating methods include roll coating, baking, air knife, spin coating, curtain coating, die coating, dip coating, roller coating, spray coating, gravure coating, reverse roll coating, air knife coating, bar coating, curtain roll coating. Dip coat, rod coat, doctor blade coat and the like.
- the energy ray curable resin such as ultraviolet rays
- the energy ray curable resin such as ultraviolet rays
- the cationic curable resins are more durable and have better adhesion
- the water-based polyurethane resin composition of the present invention Since the product is suitable for use in a cationic curing system, a cationic curing resin using a monomer and / or oligomer for a cationic curing resin and a cationic polymerization initiator is preferable.
- Examples of the monomer or oligomer for the cationic curable resin include aliphatic, aromatic or alicyclic epoxy compounds, oxetane compounds, vinyl ether compounds or oligomers thereof.
- Examples of the aliphatic epoxy compound include monofunctional epoxy compounds such as glycidyl etherified products of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, polyglycidyl etherified products of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and fats. And polyfunctional epoxy compounds such as polyglycidyl esters of group long-chain polybasic acids.
- Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, triglycidyl ether of glycerin.
- Polyglycols such as triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, dicyclopentadiene dimethanol diglycidyl ether Glycidyl ether, also propylene glycol, trimethylolpropane, glycerin, Examples thereof include polyglycidyl etherified products of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as hydrogenated bisphenol A, and diglycidyl esters of aliphatic long-chain dibasic acids.
- monoglycidyl ethers of higher aliphatic alcohols glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized polybutadiene, and the like.
- aliphatic epoxy compound a glycidyl etherified product of an aliphatic alcohol or a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof is preferable because viscosity, coating property and reactivity are improved.
- aliphatic epoxy compound commercially available products can be used.
- the aromatic epoxy compound refers to an epoxy compound containing an aromatic ring
- specific examples of the aromatic epoxy compound include a polyhydric phenol having at least one aromatic ring such as phenol, cresol, butylphenol, or the like.
- Mono / polyglycidyl etherified products of aromatic compounds having a functional hydroxyl group aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol and phenyldibutanol
- aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol and phenyldibutanol
- Glycidyl esters of polybasic aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, glycidyl esters of benzoic acid, epoxides of styrene oxide or divinylbenzene It is done.
- the aromatic epoxy compound commercially available products can be used.
- Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, ONCOAT EX-1020, ONCOAT EX-1030, ONCOAT EX-1040, ONCOAT EX-1050, ONCOAT EX-1051, ONCOAT EX-1010, ONCOAT EX-1011, ONCOAT 1012 Nagase ChemteX Corporation Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical); HP4032, HP4032D, HP4700 (DIC); ESN-475V (Toto Kasei) YX8 00 (Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (NOF Corporation); Epicron N-665, Epicron HP-7200 (DIC Corporation); EO
- the alicyclic epoxy compound refers to a compound in which an oxirane ring is directly bonded to a saturated ring without a spacer, and specific examples of the alicyclic epoxy compound include at least one alicyclic ring. Examples thereof include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by epoxidizing a polyglycidyl etherified polyhydric alcohol or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent.
- 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4 -Epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5 -Methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxy Cyclohexane), propane-2,2-diyl-bis (3,
- Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, It is preferable from the viewpoint of improving adhesion.
- alicyclic epoxy compound Commercially available products can be used as the alicyclic epoxy compound, and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 (manufactured by Daicel).
- oxetane compound examples include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and 3-ethyl-3.
- Monofunctional oxetane compounds such as-(phenoxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3-ethyl-3-[(3-triethoxysilylpropoxy) methyl] oxetane, oxetanylsilsesquioxane; 1,4-bis [ ⁇ (3-ethyl-3-oxetanyl) methoxy ⁇ methyl] benzene, 4,4′-bis [ ⁇ (3-ethyl-3-oxetanyl) methoxy ⁇ methyl] biphenyl, bis [(3- Ethyl-3-oxetanyl) methyl] ether, 1,2-bis [(3-ethyl-3- Xetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, 1,4-bis (3-
- oxetane compound commercially available products mainly composed of a cationic curable monomer can be used.
- a cationic curable monomer for example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.); Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), etanacol OXBP, OXTP (manufactured by Ube Industries).
- Examples of the vinyl ether compound include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2- Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-cyclohexanedimethanol divinyl ether.
- the cationic polymerization initiator may be any compound that can release a substance that initiates cationic polymerization by energy ray irradiation or heating, but is preferably a Lewis acid by irradiation with energy rays. Is a double salt that is an onium salt that releases bismuth or a derivative thereof. Representative examples of such compounds include the following general formula: [A] r + [B] r- Cation and anion salts represented by
- the cation [A] r + is preferably onium, and the structure thereof is, for example, the following general formula: [(R 2 ) a Q] r + Can be expressed as
- R 2 is an organic group having 1 to 60 carbon atoms and possibly containing atoms other than carbon atoms.
- a is an integer of 1 to 5.
- the a R 2 s are independent and are the same or different.
- at least one is preferably an organic group as described above having an aromatic ring.
- the anion [B] r- is preferably a halide complex, and the structure thereof is, for example, the following general formula: [LY b ] r- Can be expressed as
- L is a metal or metalloid which is a central atom of a halide complex
- B P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like.
- Y is a halogen atom.
- b is an integer of 3 to 7.
- anion [LY b ] r- of the above general formula examples include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF 4 ) ⁇ , Examples thereof include hexafluorophosphate (PF 6 ) ⁇ , hexafluoroantimonate (SbF 6 ) ⁇ , hexafluoroarsenate (AsF 6 ) ⁇ , hexachloroantimonate (SbCl 6 ) ⁇ and the like.
- the anion [B] r- is represented by the following general formula: [LY b-1 (OH)] r
- the thing of the structure represented by can also be used preferably. L, Y, and b are the same as described above.
- Other anions that can be used include perchlorate ion (ClO 4 ) ⁇ , trifluoromethylsulfite ion (CF 3 SO 3 ) ⁇ , fluorosulfonate ion (FSO 3 ) ⁇ , and toluenesulfonate anion.
- Trinitrobenzenesulfonic acid anion camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.
- onium salts it is particularly effective to use the following aromatic onium salts (a) to (c).
- aromatic onium salts (a) to (c) one of them can be used alone, or two or more can be mixed and used.
- Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc.
- Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, and tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt
- Alicyclic dicarboxylic acids trimellitic acids, trimesic acid, tricarboxylic acids such as trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid] acid anhydrides; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters And amine imide.
- Aromatic sulfonium salts having the following structure are used as cationic polymerization initiators (B ) It is more preferable to contain at least 0.1% by mass with respect to 100% by mass.
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are each independently a hydrogen atom, a halogen atom, or a carbon atom number.
- R 21 , R 22 , R 23, and R 24 each independently represents a hydrogen atom, a halogen atom, Represents an atom or an alkyl group having 1 to 10 carbon atoms, and R 25 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any one selected from the following chemical formulas (A) to (C) Represents a substituent, An q ⁇ represents a q-valent anion, and p represents a coefficient for neutralizing the charge.
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 26 , R 27 , R 28 , R 29 , R 35 , R 36 , R 37 , R 38 and R 39 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom.
- R 30 , R 31 , R 32 , R 33 and R 34 each independently represents a hydrogen atom, a halogen atom or 1 to 10 carbon atoms. Represents an alkyl group.
- the halogen atom include fluorine, chlorine, bromine and iodine.
- R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 and R 39 Is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3- Methoxypropyl, 4-methoxybutyl, 2-
- examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4- Methoxybutyloxy, 2-butyloxy, 2-butyloxy
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 26 , R 27 , R 28 R 29 , R 35 , R 36 , R 37 , R 38 and R 39 are ester groups having 2 to 10 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyl Examples thereof include oxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy and the like.
- the proportion of the cationic polymerization initiator used relative to the cationic curable component is 0.001 to 15 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the cationic curable resin component. . If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as the water absorption rate and the strength of the cured product may be adversely affected.
- Sensitizers and sensitizers include anthracene compounds and naphthalene compounds.
- anthracene compound examples include those represented by the following formula (IIIa).
- R 9 and R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms, and R 11 represents a hydrogen atom or 1 carbon atom
- R 9 and R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms
- R 11 represents a hydrogen atom or 1 carbon atom
- anthracene compound represented by the above formula (IIIa) include the following compounds.
- naphthalene compound examples include those represented by the following formula (IIIb).
- R 12 and R 13 each independently represents an alkyl group having 1 to 6 carbon atoms
- naphthalene compounds represented by the above formula (IIIb) include the following compounds.
- 4-methoxy-1-naphthol 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene and the like.
- the use ratio of the sensitizer and the sensitization aid is not particularly limited, and can be used at a general use ratio within a range that does not impair the object of the present invention.
- the total of the cationic curable resin components From the viewpoint of improving curability, the amount of the sensitizer and the sensitizer is preferably 0.1 to 3 parts by mass or more with respect to 100 parts by mass.
- the thermoplastic resin is heated and melted, and the thermoplastic resin extruded by a single screw or twin screw extruder is formed into a film by a stretching machine, and then the adhesive layer is formed on the surface of the thermoplastic resin. And a photo-curing resin is adhered on the surface.
- the manufacturing method of the water-based polyurethane resin composition of this invention is demonstrated.
- (A) a polyisocyanate component, (b) a polyol component, and (c) an anionic group introducing agent are reacted to obtain (A) a urethane prepolymer.
- a urethane prepolymer composition containing the obtained (A) urethane prepolymer and (B) a cationic curable substance is prepared.
- the urethane prepolymer composition is dispersed in water to obtain an aqueous dispersion.
- (A) urethane prepolymer in the obtained water dispersion is made to react with (C) blocking agent and / or chain extender.
- the raw materials and reaction conditions used in the method for producing the aqueous polyurethane resin composition of the present invention are as described above.
- Example 1 [Production of water-based polyurethane resin composition U-1] A five-neck separable round bottom flask equipped with a Dimroth, a stirring blade and a nitrogen line was charged with 185.23 g of isophorone diisocyanate, ETRNACOLL UH-200 (polycarbonate diol manufactured by Ube Industries, Ltd., number average molecular weight 2000) 227.99 g, trimethylolpropane.
- ETRNACOLL UH-200 polycarbonate diol manufactured by Ube Industries, Ltd., number average molecular weight 2000
- the isocyanate content of the obtained urethane prepolymer was 4.98% by mass in terms of solid content, and the acid value was 43.85 mgKOH / g in solid content.
- the obtained urethane prepolymer (including methyl ethyl ketone) was cooled to 60 ° C., and 27.78 g of triethylamine and 49.69 g of Aron oxetane OXT-221 (bis (3-ethyloxetanylmethyl) ether manufactured by Toagosei Co., Ltd.) were obtained. In addition, stirring was performed for 30 minutes to obtain a urethane prepolymer composition.
- the mass ratio of the urethane prepolymer to the Aron oxetane OXT-221 in the urethane prepolymer composition was 90/10.
- 1020.0 g of water at 40 ° C. and Adecanate B-1016 defoaming agent manufactured by ADEKA
- 620 g of the urethane prepolymer composition was added for 2 minutes. And stirred for 30 minutes.
- 80.8g of diethylamine / water (mass ratio 1/3) aqueous solution was added, and also it stirred for 30 minutes. Thereafter, the mixture was heated to 40 ° C.
- aqueous polyurethane resin composition U-1 having a solid content of 30% by mass.
- the ratio of the isocyanate reactive group equivalent contained in diethylamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.
- Example 2 [Production of water-based polyurethane resin composition U-2] A urethane prepolymer composition was obtained in the same manner as in Example 1. To a 2 L disposable cup, 1020.0 g of water at 40 ° C. and Adecanate B-1016 (defoaming agent manufactured by ADEKA) were added and stirred with a disper for 5 minutes, and then 620 g of the obtained urethane prepolymer composition was added. Added over 2 minutes and stirred for 30 minutes. Thereafter, 33.6 g of an aqueous solution of ethylenediamine / water (mass ratio 1/3) was added, and the mixture was further stirred for 30 minutes. Thereafter, the mixture was heated to 40 ° C.
- Adecanate B-1016 defoaming agent manufactured by ADEKA
- aqueous polyurethane resin composition U-2 having a solid content of 30% by mass.
- the ratio of the isocyanate reactive group equivalent contained in ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.68.
- Example 3 [Production of water-based polyurethane resin composition U-3]
- the urethane prepolymer (including methyl ethyl ketone) having an isocyanate content of 4.98% by mass in terms of solid content and an acid value of 43.85 mg KOH / g obtained in the same manner as in Example 1 was cooled to 60 ° C. 27.78 g of triethylamine and 49.69 g of 1,3,5-tris [6- (3-ethyloxetane-3-yloxycarbonylamino) hexyl] -s-triazine-2,4,6-trione In addition, stirring was performed for 30 minutes to obtain a urethane prepolymer composition.
- Example 4 [Production of water-based polyurethane resin composition U-4]
- the isocyanate content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value was 43.85 mg KOH / g of urethane prepolymer (including methyl ethyl ketone) in terms of solid content.
- 27.78 g of triethylamine and 49.69 g of ETERNACOLLOXBP (4,4′-bis [ ⁇ (3-ethyl-3-oxetanyl) methoxy ⁇ methyl] biphenyl) manufactured by Ube Industries, Ltd.) were added and stirred for 30 minutes.
- a urethane prepolymer composition was obtained.
- the mass ratio of the urethane prepolymer in the urethane prepolymer composition to 4,4′-bis [ ⁇ (3-ethyl-3-oxetanyl) methoxy ⁇ methyl] biphenyl was 90/10.
- an aqueous polyurethane resin composition U-4 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2.
- the ratio of the isocyanate reactive group equivalent contained in ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.68.
- Example 5 [Production of water-based polyurethane resin composition U-5]
- the isocyanate content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value was 43.85 mg KOH / g of urethane prepolymer (including methyl ethyl ketone) in terms of solid content.
- 27.78 g of triethylamine and 49.69 g of bisphenol A di ⁇ -methylglycidyl ether were added and stirred for 30 minutes to obtain a urethane prepolymer composition.
- the mass ratio of the urethane prepolymer to the bisphenol A di ⁇ -methylglycidyl ether in the urethane prepolymer composition was 90/10.
- an aqueous polyurethane resin composition U-5 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2.
- the ratio of the isocyanate reactive group equivalent contained in ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.
- Example 6 [Production of water-based polyurethane resin composition U-6]
- the isocyanate content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value was 43.85 mg KOH / g of urethane prepolymer (including methyl ethyl ketone) in terms of solid content.
- 27.78 g of triethylamine and 49.69 g of Celoxide 2021P manufactured by Daicel Corporation 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) were added and stirred for 30 minutes to make a urethane prepolymer composition Got.
- the mass ratio of the urethane prepolymer in the urethane prepolymer composition to 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate was 90/10.
- an aqueous polyurethane resin composition U-6 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2.
- the ratio of the isocyanate reactive group equivalent contained in ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.
- Example 7 [Production of water-based polyurethane resin composition U-7]
- the isocyanate content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value was 43.85 mg KOH / g of urethane prepolymer (including methyl ethyl ketone) in terms of solid content.
- 27.78 g of triethylamine and 49.69 g of TEPIC-VL (manufactured by Nissan Chemical Co., Ltd.) were added and stirred for 30 minutes to obtain a urethane prepolymer composition.
- the mass ratio of the urethane prepolymer to the triglycidyl isocyanurate in the urethane prepolymer composition was 90/10.
- an aqueous polyurethane resin composition U-7 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2.
- the ratio of the isocyanate reactive group equivalent contained in ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.
- Example 8 [Production of water-based polyurethane resin composition U-8] A 5-neck separable round bottom flask equipped with a Dimroth, a stirring blade, and a nitrogen line was charged with 144.31 g of isophorone diisocyanate, 177.63 g of ETERNACOLL UH-200 (polycarbonate diol, Ube Industries, Ltd., number average molecular weight 2000), trimethylolpropane.
- the ratio of the total isocyanate group equivalent (NCO) of isophorone diisocyanate to the total hydroxyl group equivalent (OH) of polycarbonate diol, trimethylolpropane and dimethylolpropionic acid, NCO / OH was 1.5.
- the obtained urethane prepolymer was cooled to 60 ° C., and 28.83 g of triethylamine and 197.14 g of Aron Oxetane OXT-221 (Tosu Gosei Co., Ltd. bis (3-ethyloxetanylmethyl) ether) were added for 30 minutes. Stirring was performed to obtain a urethane prepolymer composition.
- the mass ratio of urethane prepolymer to Aron oxetane OXT-221 in the urethane prepolymer composition was 50/50.
- the solid content was 30 through the same water dispersion step as in Example 1 except that the addition amount of diethylamine / water (mass ratio 1/3) aqueous solution was changed to 62.8 g.
- a mass% aqueous polyurethane resin composition HU-8 was obtained.
- the ratio of the isocyanate reactive group equivalent contained in diethylamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.67.
- Example 9 [Production of water-based polyurethane resin composition U-9] A urethane prepolymer composition was obtained in the same manner as in Example 1. To a 2 L disposable cup, 1020.0 g of water at 40 ° C. and Adecanate B-1016 (defoaming agent manufactured by ADEKA) were added and stirred with a disper for 5 minutes, and then 620 g of the obtained urethane prepolymer composition was added. Added over 2 minutes and stirred for 30 minutes. Thereafter, 97.2 g of an aqueous solution of adipic acid dihydrazide / water (mass ratio 1/3) was added, and the mixture was further stirred for 30 minutes. Thereafter, the mixture was heated to 40 ° C.
- Adecanate B-1016 defoaming agent manufactured by ADEKA
- aqueous polyurethane resin composition U-9 having a solid content of 30% by mass.
- the ratio of the isocyanate reactive group equivalent contained in adipic acid dihydrazide to the isocyanate group equivalent contained in the urethane prepolymer was 0.68.
- Comparative Example 1 [Production of water-based polyurethane resin composition HU-1]
- the isocyanate content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value was 43.85 mg KOH / g of urethane prepolymer (including methyl ethyl ketone) in terms of solid content.
- 27.78 g of triethylamine was added and stirred for 30 minutes to obtain a urethane prepolymer composition.
- an aqueous polyurethane resin composition HU-1 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 1.
- the ratio of the isocyanate reactive group equivalent contained in diethylamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.62.
- Comparative Example 2 [Production of water-based polyurethane resin composition HU-2]
- the urethane content obtained in the same manner as in Example 1 was 4.98% by mass in terms of solid content, and the acid value was 43.85 mg KOH / g of solid content, cooled to 60 ° C., and 27.78 g of triethylamine was obtained. And stirred for 30 minutes to obtain a urethane prepolymer composition.
- an aqueous polyurethane resin composition HU-2 having a solid content of 30% by mass was obtained through the same water dispersion step as in Example 2.
- the ratio of the isocyanate reactive group equivalent contained in ethylenediamine to the isocyanate group equivalent contained in the urethane prepolymer was 0.63.
- Comparative Example 3 [Production of water-based polyurethane resin composition HU-3] A five-neck separable round bottom flask equipped with a Dimroth, stirring blade, and nitrogen line was charged with 185.23 g of isophorone diisocyanate, ETRNACOLL UH-200 (polycarbonate diol manufactured by Ube Industries, Ltd., number average molecular weight 2000) 227.99 g, trimethylolpropane.
- ETRNACOLL UH-200 polycarbonate diol manufactured by Ube Industries, Ltd., number average molecular weight 2000
- Evaluation 1 storage stability
- the aqueous urethane resin composition was put in a sealed container and stored at 40 ° C. for up to one week, and precipitation and gelation were observed to evaluate storage stability.
- those that precipitated and gelled in less than one week indicate the number of days, those that precipitated and gelled in less than one day were marked with x, and those that did not precipitate and gelled in one week or more were marked with ⁇ .
- Evaluation 2 base material adhesion
- a water-based polyurethane resin composition was applied to the corona-treated PET surface using a bar coater so that the film thickness after drying was about 1 ⁇ m, and then dried at room temperature for 30 minutes and at 120 ° C. for 10 minutes. Got.
- the obtained test piece was cut into 100 squares using a cutter guide with a gap interval of 1 mm. Thereafter, a cellophane tape was affixed and rubbed into close contact, and then the peel-off operation was performed three times. Then, the number of remaining cells was counted to determine the adhesion. Moreover, what peeled partially in the mass was regarded as the peeled mass.
- the evaluation criteria are as follows. A: 100 left, B: 99-90 left, C: 89-80 left, D: 79-70 left, E: 69-50 left, F: 50 left left.
- Evaluation 3 Adhesion with top-coated UV-curable resin paint
- 3 ′, 4′- Apply UV curable resin paint obtained from 30 parts by mass of epoxycyclohexylmethyl ⁇ 3,4-epoxycyclohexanecarboxylate, 40 parts by mass of bisphenol A diglycidyl ether, and 5% by mass of 50% by mass propylene carbonate solution of triphenylsulfonium.
- test piece was cut into 100 squares using a cutter guide with a gap interval of 1 mm. Thereafter, a cellophane tape was affixed, rubbed and adhered, and then the work of peeling off was performed three times. Then, the number of remaining cells was counted to determine the topcoat UV adhesion. Moreover, what peeled partially in the mass was regarded as the peeled mass.
- the evaluation criteria are as follows. A: 100 left, B: 99-90 left, C: 89-80 left, D: 79-70 left, E: 69-50 left, F: 50 left left.
- the water-based polyurethane resin composition according to the present invention has excellent storage stability, and excellent adhesion to a substrate, particularly to an ultraviolet curable resin layer used as a top coating. It is suitable as an adhesive for optical films.
- the water-based polyurethane resin composition of the present invention is excellent in storage stability and adhesiveness to various substrates, in particular, from an energy ray curable resin system cured by ultraviolet rays or the like, particularly from a cationic photo-curable resin composition. Since it is excellent in adhesiveness to the layer to be formed, it can be suitably used as an adhesive for optical films.
Abstract
Description
本発明で使用される(a)成分であるポリイソシアネート成分としては、公知のポリイソシアネート成分を特に制限なく使用することができる。(a)ポリイソシアネート成分は、得られるポリウレタン分子及びこれから得られる塗膜の加水分解性に優れることから、ジイソシアネートを含有することが好ましい。ジイソシアネートとしては、例えば、トリレンジイソシアネート、ジフェニルメタン-4,4‘-ジイソシアネート、p-フェニレンジイソシアネート、キシリレンジイソシアネート、1,5-ナフチレンジイソシアネート、3,3’-ジメチルジフェニル-4,4‘-ジイソシアネート、ジアニシジンジイソシアネート、テトラメチルキシリレンジイソシアネート等の芳香族ジイソシアネート;イソホロンジイソシアネート、ジシクロヘキシルメタン-4,4’-ジイソシアネート、トランス-1,4-シクロヘキシルジイソシアネート、ノルボルネンジイソシアネート等の脂環式ジイソシアネート;1,6-ヘキサメチレンジイソシアネート、2,2,4及び/又は(2,4,4)-トリメチルヘキサメチレンジイソシアネート、リシンジイソシアネート等の脂肪族ジイソシアネートなどがあげられ、特に、これらのジイソシアネートの中でも、得られるポリウレタン分子及びこれから得られる塗膜の加水分解性に優れるので、脂環式ジイソシアネートが好ましく、イソホロンジイソシアネート、ジシクロヘキシルメタン-4、4‘-ジイソシアネートがより好ましい。これらのジイソシアネートは単独で用いることもできるし、2種以上を併用して用いることもできる。
上記のジイソシアネートは、カルボジイミド変性、イソシアヌレート変性、ビウレット変性等の変性物の形で用いることができ、各種ブロッキング剤によってブロックされたブロックイソシアネートの形で用いることができる。
また、本発明で使用される(a)成分であるポリイソシアネート成分は、1分子中にイソシアネート基を3つ以上有するポリイソシアネートを含有する場合がある。1分子中にイソシアネート基を3つ以上有するポリイソシアネートとしては、例えば、上記例示のジイソシアネートのイソシアヌレート三量化物、ビューレット三量化物、トリメチロールプロパンアダクト化物等;トリフェニルメタントリイソシアネート、1-メチルベンゾール-2,4,6-トリイソシアネート、ジメチルトリフェニルメタンテトライソシアネート等があげられ、これらのイソシアネート化合物はカルボジイミド変性、イソシアヌレート変性、ビウレット変性等の形で用いてもよく、各種のブロッキング剤によってブロックされたブロックイソシアネートの形で用いることができる。これらは単独で用いることもできるし、2種以上を併用して用いることもできる。
ここで、(a)成分であるポリイソシアネート成分において、ジイソシアネートの含有量は、50質量%より小さいと保存安定性が低下するおそれがあるので、50質量%以上が好ましく、70質量%以上がより好ましい。
(b)成分であるポリオール成分におけるポリカーボネートジオールの含有量は、(b)成分であるポリオール成分の中で好ましくは50質量%以上、より好ましくは70質量%である。
本発明に使用されるウレタンプレポリマーは末端がイソシアネート基であることが好ましいことから、NCO/OHを1.0より大きくなるように調整することが好ましく、より好ましくは1.1~2.5の範囲、更に好ましくは1.2~2.0の範囲となるように調整される。NCO/OHが1.0以下、特に1.1未満である場合には、得られたウレタンプレポリマーが高分子量化して水分散性が低下するとともに、封鎖剤及び/又は鎖延長剤と反応するためのNCO基が少なくなり、得られる水系ポリウレタン樹脂組成物の保存安定性に悪影響するおそれがある。NCO/OHが2.0よりも大きい場合には、得られたプレポリマーの水分散時にイソシアネート基と水とが反応することによって二酸化炭素が発生して急激な発泡などの製造時の問題を引き起こすおそれがあり、水系ポリウレタン樹脂組成物とした場合にも基材との密着性などの性能低下のおそれがあるため好ましくない。
尚、上述の(A)成分であるウレタンプレポリマーの酸価は、(A)成分であるウレタンプレポリマーの反応成分の配合量から求めた理論値である。後述の様に(A)成分であるウレタンプレポリマーの製造に不活性溶媒を用いた場合には、得られる(A)成分であるウレタンプレポリマーの酸価の測定値は上述の理論値から変動する。上述の理論値と測定値と理論値との間には以下の関係がある。
酸価(理論値)=酸価(測定値)×〔(a)+(b)+(c)+溶媒:質量合計〕/〔(a)+(b)+(c):質量合計〕
これらの触媒の使用量に制限はないが、(a)成分、(b)成分及び(c)成分の総量に対して、好ましくは0.001~1質量%、より好ましくは0.01~0.1質量%である。
これらの架橋剤を使用する場合の使用量は、(a)成分であるポリオール100質量部に対して、好ましくは0.01~10質量部であり、更に好ましくは0.1~5質量部である。
ここで使用される不活性溶媒としては、水に親和性の大きいアセトン、メチルエチルケトン、ジオキサン、テトラヒドロフラン、N-メチル-2-ピロリドンなどがあげられる。
沸点100℃以下の溶媒を使用する場合には、本発明の水系ポリウレタン樹脂組成物を製造した後に、その溶媒を減圧留去等によって除去することが好ましい。
溶媒の使用量は特に制限はないが、(A)成分であるウレタンプレポリマーの原料の全量100質量部に対して、3~200質量部が好ましい。
これらは単独で用いることもできるし、2種以上を併用して用いることもできる。
本発明の水系ポリウレタン樹脂組成物の乾燥物の耐候性、耐水性などが良好であるという観点から、熱によって容易に解離する揮発性の高いアニオン性基中和剤の使用が好ましい。特に、トリメチルアミン、トリエチルアミンが好ましい。
これらの中でも水溶性の二級アミン、特に、ジエチルアミンが好ましい。
これの鎖伸長剤の中でも、エチレンジアミンなどの活性水素を2個以上有する水溶性のアミン化合物あるいは水溶性のジカルボン酸ジヒドラジドが好ましい。
本発明において、(C)成分として鎖伸長剤を単独で使用する場合、鎖伸長剤の使用量は、鎖伸長前の(A)成分であるウレタンプレポリマーに含まれるイソシアネート基当量に対する、鎖伸長剤に含まれるイソシアネート反応基当量の比が0.1~1.0の範囲となる量に設定することが好ましい。
本発明において、(C)成分として封鎖剤及び鎖伸長剤を使用する場合、封鎖剤及び鎖伸長剤の使用量は、封鎖及び鎖伸長前の(A)成分であるウレタンプレポリマーに含まれるイソシアネート基当量に対する、封鎖剤及び鎖伸長剤に含まれるイソシアネート反応基当量の比が0.1~1.0の範囲となる量に設定することが好ましい。
また、これらの各種添加剤の添加方法は、ポリオール成分に添加する方法、プレポリマーに添加する方法、水分散時に水相に添加する方法、水分散後に添加する方法などがあげられるが、それぞれ適した方法を選択することができる。
尚、プラスチック基材に、コロナ放電処理、火炎処理、紫外線処理、高周波処理、グロー放電処理、活性プラズマ処理、レーザー処理、ブラスト処理などの表面活性化処理を行うことができる。
脂肪族エポキシ化合物としては、脂肪族アルコールのグリシジルエーテル化物あるいは脂肪族多価アルコール又はそのアルキレンオキサイド付加物のポリグリシジルエーテル化物が、粘度、塗工性及び反応性が向上するので好ましい。
脂環式エポキシ化合物としては、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート又は3,4-エポキシ-1-メチルシクロヘキシル-3,4-エポキシ-1-メチルヘキサンカルボキシレートが、密着性向上の観点から好ましい。
[A]r+[B]r-
で表される陽イオンと陰イオンの塩をあげることができる。
[(R2)aQ]r+
で表すことができる。
[LYb]r-
で表すことができる。
[LYb-1(OH)]r
で表される構造のものも好ましく用いることができる。L,Y,bは上記と同様である。また、その他用いることのできる陰イオンとしては、過塩素酸イオン(ClO4)-、トリフルオロメチル亜硫酸イオン(CF3SO3)-、フルオロスルホン酸イオン(FSO3)-、トルエンスルホン酸陰イオン、トリニトロベンゼンスルホン酸陰イオン、カンファースルフォネート、ノナフロロブタンスルフォネート、ヘキサデカフロロオクタンスルフォネート、テトラアリールボレート、テトラキス(ペンタフルオロフェニル)ボレート等をあげることができる。
9,10-ジエトキシアントラセン、
9,10-ジプロポキシアントラセン、
9,10-ジイソプロポキシアントラセン、
9,10-ジブトキシアントラセン、
9,10-ジペンチルオキシアントラセン、
9,10-ジヘキシルオキシアントラセン、
9,10-ビス(2-メトキシエトキシ)アントラセン、
9,10-ビス(2-エトキシエトキシ)アントラセン、
9,10-ビス(2-ブトキシエトキシ)アントラセン、
9,10-ビス(3-ブトキシプロポキシ)アントラセン、
2-メチル-又は2-エチル-9,10-ジメトキシアントラセン、
2-メチル-又は2-エチル-9,10-ジエトキシアントラセン、
2-メチル-又は2-エチル-9,10-ジプロポキシアントラセン、
2-メチル-又は2-エチル-9,10-ジイソプロポキシアントラセン、
2-メチル-又は2-エチル-9,10-ジブトキシアントラセン、
2-メチル-又は2-エチル-9,10-ジペンチルオキシアントラセン、
2-メチル-又は2-エチル-9,10-ジヘキシルオキシアントラセンなど。
4-エトキシ-1-ナフトール、
4-プロポキシ-1-ナフトール、
4-ブトキシ-1-ナフトール、
4-ヘキシルオキシ-1-ナフトール、
1,4-ジメトキシナフタレン、
1-エトキシ-4-メトキシナフタレン、
1,4-ジエトキシナフタレン、
1,4-ジプロポキシナフタレン、
1,4-ジブトキシナフタレンなど。
本発明の水系ポリウレタン樹脂組成物の製造方法は、(a)ポリイソシアネート成分、(b)ポリオール成分及び(c)アニオン性基導入剤を反応させて(A)ウレタンプレポリマーを得る。得られた(A)ウレタンプレポリマーと(B)カチオン硬化性物質とを含むウレタンプレポリマー組成物を調製する。次いで、上記ウレタンプレポリマー組成物を水中に分散させて水分散を得る。そして、得られた水分散中の(A)ウレタンプレポリマーを(C)封鎖剤及び/又は鎖伸長剤と反応させる。
本発明の水系ポリウレタン樹脂組成物の製造方法において用いられる原料や反応条件等は上述したとおりである。
ジムロート、撹拌羽根、窒素ラインを装着した5口セパラブル丸底フラスコに、イソホロンジイソシアネート185.23g、ETERNACOLL UH-200(宇部興産(株)製ポリカーボネートジオール、数平均分子量2000)227.99g、トリメチロールプロパン6.69g、ジメチロールプロピオン酸49.16g、アデカスタブOT-1((株)ADEKA製ジオクチル錫ラウレート)0.55gをメチルエチルケトン202.98gに加えて、80℃で6時間反応させウレタンプレポリマーを得た。イソホロンジイソシアネートの全イソシアネート基当量(NCO)と、ポリカーボネートジオール、トリメチロールプロパン及びジメチロールプロピオン酸の全水酸基当量(OH)との比、NCO/OHは1.5であった。得られたウレタンプレポリマーのイソシアネート含有量は固形分換算で4.98質量%、酸価は固形分で43.85mgKOH/gであった。
得られたウレタンプレポリマー(メチルエチルケトン含む)を60℃まで冷却し、トリエチルアミン27.78gと、アロンオキセタンOXT-221(東亞合成(株)製ビス(3-エチルオキセタニルメチル)エーテル)49.69gとを加え、30分間撹拌を行いウレタンプレポリマー組成物を得た。ウレタンプレポリマー組成物中のウレタンプレポリマーとアロンオキセタンOXT-221との質量比は90/10であった。
2Lのディスポカップに、40℃の水を1020.0g、アデカネートB-1016((株)ADEKA製消泡剤)を加え、ディスパーで5分間撹拌した後、上記ウレタンプレポリマー組成物620gを2分間かけて加え、30分間撹拌した。その後、ジエチルアミン/水(質量比1/3)水溶液を80.8g加え、更に30分間撹拌を行った。その後、40℃に加温し、減圧条件下でメチルエチルケトンを除去し、固形分30質量%の水系ポリウレタン樹脂組成物U-1を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、ジエチルアミンに含まれるイソシアネート反応基当量の比は0.67であった。
実施例1と同様にしてウレタンプレポリマー組成物を得た。
2Lのディスポカップに、40℃の水を1020.0g、アデカネートB-1016((株)ADEKA製消泡剤)を加え、ディスパーで5分間撹拌した後、得られたウレタンプレポリマー組成物620gを2分間かけて加え、30分間撹拌した。その後、エチレンジアミン/水(質量比1/3)水溶液を33.6g加え、更に30分間撹拌を行った。その後、40℃に加温し、減圧条件下でメチルエチルケトンを除去し、固形分30質量%の水系ポリウレタン樹脂組成物U-2を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、エチレンジアミンに含まれるイソシアネート反応基当量の比は0.68であった。
実施例1と同様にして得られた、イソシアネート含有量は固形分換算で4.98質量%、酸価は固形分で43.85mgKOH/gのウレタンプレポリマー(メチルエチルケトンを含む)を60℃まで冷却し、トリエチルアミン27.78gと、1,3,5-トリス〔6-(3-エチルオキセタン-3-イルオキシカルボニルアミノ)ヘキシル〕-s-トリアジン-2,4,6-トリオン49.69gとを加え、30分間撹拌を行いウレタンプレポリマー組成物を得た。ウレタンプレポリマー組成物中のウレタンプレポリマーと1,3,5-トリス〔6-(3-エチルオキセタン-3-イルオキシカルボニルアミノ)ヘキシル〕-s-トリアジン-2,4,6-トリオンとの質量比は90/10であった。
ここで得られたウレタンプレポリマー組成物を用いて、実施例2と同様の水分散工程を経て固形分30質量%の水系ポリウレタン樹脂組成物U-3を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、エチレンジアミンに含まれるイソシアネート反応基当量の比は0.68であった。
実施例1と同様にして得られたイソシアネート含有量は固形分換算で4.98質量%、酸価は固形分で43.85mgKOH/gのウレタンプレポリマー(メチルエチルケトンを含む)を60℃まで冷却し、トリエチルアミン27.78gと、ETERNACOLLOXBP(宇部興産(株)製4,4‘-ビス〔{(3-エチル-3-オキセタニル)メトキシ}メチル〕ビフェニル)49.69gとを加え、30分間撹拌を行いウレタンプレポリマー組成物を得た。ウレタンプレポリマー組成物中のウレタンプレポリマーと4,4‘-ビス〔{(3-エチル-3-オキセタニル)メトキシ}メチル〕ビフェニルとの質量比は90/10であった。
ここで得られたウレタンプレポリマー組成物を用いて、実施例2と同様の水分散工程を経て固形分30質量%の水系ポリウレタン樹脂組成物U-4を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、エチレンジアミンに含まれるイソシアネート反応基当量の比は0.68であった。
実施例1と同様にして得られたイソシアネート含有量は固形分換算で4.98質量%、酸価は固形分で43.85mgKOH/gのウレタンプレポリマー(メチルエチルケトンを含む)を60℃まで冷却し、トリエチルアミン27.78gと、ビスフェノールAジβ-メチルグリシジルエーテル49.69gとを加え、30分間撹拌を行いウレタンプレポリマー組成物を得た。ウレタンプレポリマー組成物中のウレタンプレポリマーとビスフェノールAジβ-メチルグリシジルエーテルとの質量比は90/10であった。
ここで得られたウレタンプレポリマー組成物を用いて、実施例2と同様の水分散工程を経て固形分30質量%の水系ポリウレタン樹脂組成物U-5を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、エチレンジアミンに含まれるイソシアネート反応基当量の比は0.67であった。
実施例1と同様にして得られたイソシアネート含有量は固形分換算で4.98質量%、酸価は固形分で43.85mgKOH/gのウレタンプレポリマー(メチルエチルケトンを含む)を60℃まで冷却し、トリエチルアミン27.78gと、セロキサイド2021P((株)ダイセル製3‘,4’-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレート)49.69gとを加え、30分間撹拌を行いウレタンプレポリマー組成物を得た。ウレタンプレポリマー組成物中のウレタンプレポリマーと3‘,4’-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレートとの質量比は90/10であった。
ここで得られたウレタンプレポリマー組成物を用いて、実施例2と同様の水分散工程を経て固形分30質量%の水系ポリウレタン樹脂組成物U-6を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、エチレンジアミンに含まれるイソシアネート反応基当量の比は0.67であった。
実施例1と同様にして得られたイソシアネート含有量は固形分換算で4.98質量%、酸価は固形分で43.85mgKOH/gのウレタンプレポリマー(メチルエチルケトンを含む)を60℃まで冷却し、トリエチルアミン27.78gと、TEPIC-VL(日産化学(株)社製 トリグリシジルイソシアヌレート)49.69gとを加え、30分間撹拌を行いウレタンプレポリマー組成物を得た。ウレタンプレポリマー組成物中のウレタンプレポリマーとトリグリシジルイソシアヌレートとの質量比は90/10であった。
ここで得られたウレタンプレポリマー組成物を用いて、実施例2と同様の水分散工程を経て固形分30質量%の水系ポリウレタン樹脂組成物U-7を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、エチレンジアミンに含まれるイソシアネート反応基当量の比は0.67であった。
ジムロート、撹拌羽根、窒素ラインを装着した5口セパラブル丸底フラスコに、イソホロンジイソシアネート144.31g、ETERNACOLL UH-200(宇部興産(株)製ポリカーボネートジオール、数平均分子量2000)177.63g、トリメチロールプロパン5.21g、ジメチロールプロピオン酸38.30g、アデカスタブOT-1((株)ADEKA製オクチル錫ラウレート)0.55gをメチルエチルケトン158.14gに加えて、80℃で6時間反応させイソシアネート含有量は固形分換算で4.98質量%、酸価は固形分で43.85mgKOH/gのウレタンプレポリマーを得た。イソホロンジイソシアネートの全イソシアネート基当量(NCO)と、ポリカーボネートジオール、トリメチロールプロパン及びジメチロールプロピオン酸の全水酸基当量(OH)との比、NCO/OHは1.5であった。
得られたウレタンプレポリマーを60℃まで冷却し、トリエチルアミン28.83gと、アロンオキセタンOXT-221(東亞合成(株)製ビス(3-エチルオキセタニルメチル)エーテル)197.14gとを加え、30分間撹拌を行いウレタンプレポリマー組成物を得た。ウレタンプレポリマー組成物中のウレタンプレポリマーとアロンオキセタンOXT-221との質量比は50/50であった。
ここで得られたウレタンプレポリマー組成物を用いて、ジエチルアミン/水(質量比1/3)水溶液の添加量を62.8gとした以外は実施例1と同様の水分散工程を経て固形分30質量%の水系ポリウレタン樹脂組成物HU-8を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、ジエチルアミンに含まれるイソシアネート反応基当量の比は0.67であった。
実施例1と同様にしてウレタンプレポリマー組成物を得た。
2Lのディスポカップに、40℃の水を1020.0g、アデカネートB-1016((株)ADEKA製消泡剤)を加え、ディスパーで5分間撹拌した後、得られたウレタンプレポリマー組成物620gを2分間かけて加え、30分間撹拌した。その後、アジピン酸ジヒドラジド/水(質量比1/3)水溶液を97.2g加え、更に30分間撹拌を行った。その後、40℃に加温し、減圧条件下でメチルエチルケトンを除去し、固形分30質量%の水系ポリウレタン樹脂組成物U-9を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、アジピン酸ジヒドラジドに含まれるイソシアネート反応基当量の比は0.68であった。
実施例1と同様にして得られたイソシアネート含有量は固形分換算で4.98質量%、酸価は固形分で43.85mgKOH/gのウレタンプレポリマー(メチルエチルケトンを含む)を60℃まで冷却し、トリエチルアミン27.78gを加え、30分間撹拌を行いウレタンプレポリマー組成物を得た。
ここで得られたウレタンプレポリマー組成物を用いて、実施例1と同様の水分散工程を経て固形分30質量%の水系ポリウレタン樹脂組成物HU-1を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、ジエチルアミンに含まれるイソシアネート反応基当量の比は0.62であった。
実施例1と同様にして得られたイソシアネート含有量は固形分換算で4.98質量%、酸価は固形分で43.85mgKOH/gのウレタンプレポリマーを60℃まで冷却し、トリエチルアミン27.78gを加え、30分間撹拌を行いウレタンプレポリマー組成物を得た。
ここで得られたウレタンプレポリマー組成物を用いて、実施例2と同様の水分散工程を経て固形分30質量%の水系ポリウレタン樹脂組成物HU-2を得た。上記ウレタンプレポリマーに含まれるイソシアネート基当量に対する、エチレンジアミンに含まれるイソシアネート反応基当量の比は0.63であった。
ジムロート、撹拌羽根、窒素ラインを装着した5口セパラブル丸底フラスコに、イソホロンジイソシアネート185.23g、ETERNACOLL UH-200(宇部興産(株)製ポリカーボネートジオール、数平均分子量2000)227.99g、トリメチロールプロパン6.69g、ジメチロールプロピオン酸49.16g、アデカスタブOT-1((株)(ADEKA製オクチル錫ラウレート)0.55gをメチルエチルケトン202.98gに加えて、80℃で6時間反応させイソシアネート含有量は固形分換算で4.98質量%、酸価は固形分で43.85mgKOH/gのウレタンプレポリマーを得た。
得られたウレタンプレポリマーを60℃まで冷却し、トリエチルアミン27.78gと、30分間撹拌を行いウレタンプレポリマー組成物を得た。
2Lのディスポカップに、40℃の水を1020.0g、アデカネートB-1016((株)ADEKA製消泡剤)を加え、ディスパーで5分間撹拌した後、上記ウレタンプレポリマー組成物558gを2分間かけて加え、30分間撹拌した。その後、ジエチルアミン/水(質量比1/3)水溶液を80.8g加え、更に30分間撹拌を行った。更に、アロンオキセタンOXT-221(東亞合成(株)製ビス(3-エチルオキセタニルメチル)エーテル)62gを加え、30分間撹拌した。その後、40℃に加温し、減圧条件下でメチルエチルケトンを除去したところ均一な分散物は得られず、水系ポリウレタン樹脂組成物HU-3は製造することができなかった。
水系ウレタン樹脂組成物を密閉容器に入れ、40℃で最大一週間まで保存して、沈殿、ゲル化を観察して保存安定性を評価した。表に、一週間未満で沈殿、ゲル化したものはその日数を示し、一日未満で沈殿、ゲル化するものを×とし、一週間以上沈殿、ゲル化しないものを○とした。
コロナ処理PET表面に、乾燥後の膜厚が約1umとなるようにバーコーターを用いて、水系ポリウレタン樹脂組成物を塗布し、その後、室温で30分、120℃で10分乾燥し、試験片を得た。
得られた試験片に隙間間隔1mmのカッターガイドを用いて、100マスにカットした。その後セロハンテープを貼付し、こすって密着させたのちに、勢いよくはがす作業を3回行った後、残存したマスの数を数え、密着性を求めた。またマスの中で部分的に剥離しているものは剥離したマスとしてとらえた。評価基準は以下のとおりである。
A:100個残り、B:99~90個残り、C:89~80個残り、D:79~70個残り、E:69~50個以下残り、F:50個以下残り
上記評価2で得られた試験片のウレタン膜側に硬化後の膜厚が3umとなるようにバーコーターを用いて、1,6-ヘキサンジオールジグリシジルエーテル30質量部、3‘,4’-エポキシシクロヘキシルメチル・3,4-エポキシシクロヘキサンカルボキシレート30質量部、ビスフェノールAジグリシジルエーテル40質量部、及びトリフェニルスルホニウムのプロピレンカーボネート50質量%溶液5質量%から得られた紫外線硬化性樹脂塗料を塗布し、メタルハライドランプを用いて、強度600mW/cm2、積算光量1000mJ/cm2のUV照射して硬化させ、試験片を得た。
得られた試験片に隙間間隔1mmのカッターガイドを用いて、100マスにカットした。その後セロハンテープを貼付し、こすって密着させたのちに、勢いよくはがす作業を3回行った後、残存したマスの数を数え、上塗りUV密着性を求めた。またマスの中で部分的に剥離しているものは剥離したマスとしてとらえた。評価基準は以下のとおりである。
A:100個残り、B:99~90個残り、C:89~80個残り、D:79~70個残り、E:69~50個以下残り、F:50個以下残り
Claims (7)
- (a)ポリイソシアネート成分、(b)ポリオール成分及び(c)アニオン性基導入剤を反応させてなる(A)ウレタンプレポリマーと、(B)カチオン硬化性物質とを含むウレタンプレポリマー組成物を水中に分散させて水分散を得、得られた水分散中の(A)ウレタンプレポリマーを(C)封鎖剤及び/又は鎖伸長剤と反応させることによって得られる、水系ポリウレタン樹脂組成物。
- (B)成分であるカチオン硬化性物質がオキセタン化合物及びエポキシ化合物の中から選ばれる少なくとも一種である、請求項1記載の水系ポリウレタン樹脂組成物。
- (B)成分であるカチオン硬化性物質が、オキセタン化合物である、請求項2に記載の水系ポリウレタン樹脂組成物。
- (B)成分であるカチオン硬化性物質が、β-アルキルグリシジル化合物である、請求項2に記載の水系ポリウレタン樹脂組成物。
- (C)成分である鎖伸長剤が、活性水素を2個以上有する水溶性のアミン化合物及び水溶性のジカルボン酸ジヒドラジド化合物の中から選ばれる少なくとも一種である、請求項1~4の何れか1項に記載の水系ポリウレタン樹脂組成物。
- (C)成分である封鎖剤が、水溶性の二級アミン化合物である、請求項1~4の何れかに記載の水系ポリウレタン樹脂組成物。
- (a)ポリイソシアネート成分、(b)ポリオール成分及び(c)アニオン性基導入剤を反応させてなる(A)ウレタンプレポリマーと、(B)カチオン硬化性物質とを含むウレタンプレポリマー組成物を水中に分散させて水分散を得、得られた水分散中の(A)ウレタンプレポリマーを(C)封鎖剤及び/又は鎖伸長剤と反応させる、水系ポリウレタン樹脂組成物の製造方法。
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