WO2022045022A1 - 水性樹脂架橋剤、水性樹脂架橋剤含有液及び水性樹脂組成物 - Google Patents
水性樹脂架橋剤、水性樹脂架橋剤含有液及び水性樹脂組成物 Download PDFInfo
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- WO2022045022A1 WO2022045022A1 PCT/JP2021/030668 JP2021030668W WO2022045022A1 WO 2022045022 A1 WO2022045022 A1 WO 2022045022A1 JP 2021030668 W JP2021030668 W JP 2021030668W WO 2022045022 A1 WO2022045022 A1 WO 2022045022A1
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- aqueous resin
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
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Definitions
- the present invention relates to a carbodiimide-based aqueous resin cross-linking agent, and an aqueous resin cross-linking agent-containing liquid and an aqueous resin composition containing the same.
- Water-soluble or water-dispersible water-based resins are easy to handle in terms of environment and safety, so they are used in various applications such as paints, inks, fiber treatment agents, adhesives, coating agents, and adhesives. It is used.
- a hydrophilic group such as a hydroxyl group or a carboxy group is introduced in order to impart water solubility or water dispersibility to the resin itself. Therefore, the water-based resin tends to be inferior in water resistance and durability as compared with the oil-based resin. Therefore, in order to improve various physical properties such as water resistance, durability, and strength of the water-based resin, a cross-linking agent is added to the water-based resin.
- Patent Document 1 describes storage stability when two types of polycarbodiimide compounds, including a polycarbodiimide compound having a predetermined hydrophilic group at the terminal, are mixed at a predetermined ratio and coexisted with an aqueous resin. It is described that an aqueous resin cross-linking agent having excellent cross-linking performance and maintaining cross-linking performance can be obtained even when coexisting for a long period of time.
- the present inventor focused on the carbodiimide-based cross-linking agent having excellent storage stability as described above, and repeated studies to improve the physical properties of the cured product of the aqueous resin, and made water-based. We have found an aqueous resin cross-linking agent that can improve the hardness and solvent resistance of the resin coating film.
- the present invention has excellent storage stability in an aqueous medium, excellent storage stability when coexistent with an aqueous resin, and further, the hardness and solvent resistance of a coating film for a cured product of an aqueous resin. It is an object of the present invention to provide a carbodiimide-based aqueous resin cross-linking agent which can be improved, and an aqueous resin cross-linking agent-containing liquid and an aqueous resin composition containing the same.
- a cured film having high hardness and good solvent resistance can be obtained for a cured product of the aqueous resin. It is based on what we have found.
- the present invention provides the following means.
- the polycarbodiimide compound (A) and the polycarbodiimide compound (B) are contained, and the polycarbodiimide compound (A) has a structure in which the isocyanate groups at both ends are sealed with a hydrophilic organic compound, respectively. At least one of the hydrophilic organic compounds has a molecular weight of 340 or more, and the polycarbodiimide compound (B) has a diisocyanate compound having one cyclohexyl ring or one benzene ring as a structural unit, and the isocyanate groups at both ends each have a molecular weight of 300.
- the structure is sealed with the following organic compound, and the polycarbodiimide compound (A) is 5 to 90 parts by mass in a total of 100 parts by mass of the polycarbodiimide compound (A) and the polycarbodiimide compound (B). , Aqueous resin cross-linking agent.
- the aqueous resin cross-linking agent according to the above [1], wherein the hydrophilic organic compound having a molecular weight of 340 or more is a compound represented by the following formula (1).
- R 1 (OCHR 2 CH 2 ) n OH (1) In the formula (1), R 1 is an alkyl group, a cycloalkyl group or an aryl group having 1 to 20 carbon atoms.
- R 2 is a hydrogen atom or a methyl group.
- N is a number of 7 to 30. be.
- [3] The aqueous resin cross-linking agent according to the above [2], wherein R 1 is a methyl group and R 2 is a hydrogen atom in the above formula (1).
- [4] The carbodiimide-based aqueous resin cross-linking agent according to any one of [1] to [3] above, wherein the organic compound having a molecular weight of 300 or less has one functional group that reacts with an isocyanate group.
- liquid cross-linking agent-containing liquid for an aqueous resin according to the above [10], wherein the anionic surfactant is at least one selected from alkylbenzene sulfonate, alkyl sulfate, and sodium N-cocoylmethyltaurine. ..
- aqueous resin composition containing the aqueous resin cross-linking agent according to any one of the above [1] to [6] and the aqueous resin.
- the aqueous resin is at least one selected from polyester resin, acrylic resin, polyurethane resin, epoxy resin, styrene-acrylic resin, melamine resin, polyolefin resin and fluororesin.
- aqueous resin composition according to any one of [12] to [14] above which is used for an adhesive, a fiber treatment agent, a coating agent, an ink, a paint or an adhesive.
- the aqueous resin composition according to any one of [12] to [14] above which is used for wet-on-wet coating.
- the aqueous resin cross-linking agent of the present invention is excellent in storage stability in an aqueous medium, and is also excellent in storage stability when coexistent with an aqueous resin. Further, by using the aqueous resin cross-linking agent, the hardness and solvent resistance of the coating film can be improved for the cured product of the aqueous resin. Therefore, the aqueous resin composition containing the aqueous resin cross-linking agent can be suitably used for applications such as adhesives, fiber treatment agents, coating agents, inks, paints, and pressure-sensitive adhesives.
- aqueous resin cross-linking agent of the present invention means that it has solubility or dispersibility in an aqueous medium.
- Aqueous medium shall refer to water and / or a hydrophilic solvent.
- polycarbodiimide compound refers to a compound having two or more carbodiimide groups.
- the aqueous resin cross-linking agent of the present invention contains the polycarbodiimide compound (A) and the polycarbodiimide compound (B), and the polycarbodiimide compound (A) in a total of 100 parts by mass of both is 5 to 90 parts by mass. It is a feature. That is, the aqueous resin cross-linking agent contains two kinds of polycarbodiimide compounds (A) and (B).
- the aqueous resin cross-linking agent having such a compounding composition is excellent in storage stability in an aqueous medium and also excellent in storage stability when coexistent with the aqueous resin. Hardness and solvent resistance can be improved.
- the polycarbodiimide compound (A) is a polycarbodiimide compound having a structure in which isocyanate groups at both ends are sealed with a hydrophilic organic compound, and at least one of the hydrophilic organic compounds has a molecular weight of 340 or more.
- the hydrophilic organic compound is preferably a compound having one or more functional groups reactive with an isocyanate group and having one or more heteroatoms in a structure other than the functional groups.
- the functional group include a hydroxyl group, a primary amino group, a secondary amino group, an epoxy group, an isocyanate group, a carboxy group and the like. That is, the hydrophilic organic compound has any functional group selected from a hydroxyl group, a primary amino group, a secondary amino group, an epoxy group, an isocyanate group, and a carboxy group, and other than the functional group. It is more preferable that the compound has one or more heteroatoms in the structure of.
- the hydrophilic organic compound is preferably a compound selected from monoamine, monoisocyanate, monool, monoepoxide and monocarboxylic acid. More preferably, the functional group has one hydroxyl group, a primary amino group or a secondary amino group at the end of the molecular chain, and one or more heteroatoms in a structure other than the functional group. It is a monool or a monoamine having. The monool or monoamine may have an anionic group and / or a cationic group.
- hydrophilic organic compound examples include polyoxyalkylene monoalkyl ether, monohydroxy polyester, monohydroxyalkyl sulfonate, dialkylamino alcohol, hydroxycarboxylic acid alkyl ester, dialkylaminoalkylamine, polyoxyalkylene monoamine, and polyoxy.
- examples thereof include alkylenediamine and polyoxyalkylene glycol.
- polyoxyalkylene monoalkyl ether, monohydroxy polyester, monohydroxyalkyl sulfonate, dialkylaminoalcohol, hydroxycarboxylic acid alkyl ester, dialkylaminoalkylamine, and polyoxyalkylene monoamine are preferable, and polyoxyalkylene monoalkyl ether. Is more preferable.
- hydrophilic organic compound examples include compounds represented by the following formula (1).
- R 1 is an alkyl group, a cycloalkyl group or an aryl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and for example, a methyl group or an ethyl group. Examples thereof include a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a cyclohexyl group and a phenyl group.
- R 1 is more preferably an alkyl group having 1 to 4 carbon atoms.
- R 2 is a hydrogen atom or a methyl group.
- R 1 is more preferably a methyl group, and R 2 is more preferably a hydrogen atom.
- n is a number of 1 to 30, preferably 7 to 30, more preferably 8 to 20, from the viewpoint of good hydrophilicity of the polycarbodiimide compound (A).
- the compound represented by the formula (1) may be an aggregate of molecules having different numbers of oxyalkylene groups (OCHR 2 CH 2 ). In this case, the average value of the number of oxyalkylene groups in each molecule is n.
- the compound represented by the formula (1) include polyoxyalkylene monoalkyl ethers such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, and polypropylene glycol monophenyl ether.
- polyoxyalkylene monophenyl ether and the like, and polyethylene glycol monomethyl ether is particularly preferable from the viewpoint of handleability, availability, and good hydrophilicity of the polycarbodiimide compound (A).
- the hydrophilic organic compound is a polyoxyalkylene glycol in which R 1 is a hydrogen atom or a hydroxyalkyl group in the formula (1).
- the hydrophilic organic compound when the hydrophilic organic compound is a polyoxyalkylene monoalkyl ether or polyoxyalkylene glycol, the hydrophilic organic compound may be a polyoxyalkylene group in the formula (1) [(OCHR 2 CH 2 ) n ]. However, it may have a structure such as a block copolymer of polyethylene glycol and polypropylene glycol or a random copolymer.
- monohydroxyalkyl sulfonate examples include a compound represented by the following formula (2).
- R 3 is an alkylene group having 1 to 10 carbon atoms, and specifically, a methylene group, an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and the like. Examples thereof include an octamethylene group, a nonamethylene group and a decamethylene group.
- M is an alkali metal atom, preferably Na or K.
- dialkylaminoalcohol examples include compounds represented by the following formula (3).
- R 4 is an alkyl group having 1 to 4 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, and the like. And t-butyl groups.
- R 5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, and a t-butyl group.
- dialkylaminoalcohol represented by the formula (3) include N, N-dimethylisopropanolamine, N, N-diethylisopropanolamine and the like.
- hydroxycarboxylic acid alkyl ester examples include compounds represented by the following formula (4).
- R 6 is an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
- R 7 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
- hydroxycarboxylic acid alkyl ester represented by the formula (4) include methyl glycolate, methyl lactate and the like.
- dialkylaminoalkylamine examples include compounds represented by the following formula (5).
- R 8 is an alkyl group having 1 to 4 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, and the like.
- R 9 is an alkylene group having 1 to 4 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.
- polyoxyalkylene monoamine or polyoxyalkylene diamine examples include a compound represented by the following formula (6).
- R 10 is an alkyl group or an aminoalkyl group having 1 to 4 carbon atoms.
- the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, and a t-butyl group.
- R 11 is a hydrogen atom or an alkylene group having 1 to 4 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group and a tetramethylene group.
- R 12 is an aminoalkyl group having 1 to 4 carbon atoms.
- aminoalkyl group examples include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminoisopropyl group, an amino-n-butyl group, an amino-s-butyl group, an isoaminobutyl group, and an amino-t.
- -Butyl group is mentioned.
- the polyoxyalkylene group [(OCHR 11 CH 2) n] in the formula (6) is the polyoxyalkylene group [(OCHR 11 CH 2 ) n ] in the formula (1). Similar to OCHR 2 CH 2 ) n ], it may have a structure such as a block copolymer of polyethylene glycol and polypropylene glycol or a random copolymer.
- the hydrophilic organic compound is a compound represented by the formula (1) among the compounds represented by the above formulas (1) to (6) from the viewpoint of good hydrophilicity of the polycarbodiimide compound (A).
- the polyoxyalkylene monoalkyl ether is preferable.
- the polyoxyalkylene monoalkyl ether having n of 7 to 30 in the formula (1) is used as the hydrophilic organic compound, the polyoxyalkylene monoalkyl ether having n of less than 7 in the formula (1) is used in the formula (3). It is also preferable to use in combination with one or more compounds selected from the dialkylaminoalcohol represented by the formula (4) and the hydroxycarboxylic acid alkyl ester represented by the formula (4).
- the polycarbodiimide compound (A) has a structure in which the isocyanate groups at both ends are sealed with a hydrophilic organic compound, and the hydrophilic organic compound for sealing at least one end of the isocyanate group has a molecular weight of 340 or more. be.
- the hydrophilicity of the polycarbodiimide compound (A) is improved by having the hydrophilic organic compound as the terminal encapsulant having a molecular weight of 340 or more at least at one end. From the viewpoint of better hydrophilicity, it is preferable that the terminal encapsulants at both ends are all hydrophilic organic compounds having a molecular weight of 340 or more.
- the molecular weight of the hydrophilic organic compound is preferably 350 or more, more preferably 400 or more, from the viewpoint of good hydrophilicity of the polycarbodiimide compound (A). Further, from the viewpoint of maintaining good hydrophilicity of the hydrophilic organic compound, it is preferably 3200 or less.
- the hydrophilic organic compound having a molecular weight of 340 or more the polyoxyalkylene monoalkyl ether among the compounds represented by the formula (1) is preferable. From the viewpoint of storage stability, a polyoxyalkylene monoalkyl ether having a molecular weight of 450 to 600 is more preferable.
- the hydrophilic organic compound as an end-capping agent has n of 7 to 30 in the formula (1) and has the same or different polyoxy having a molecular weight of 340 or more. It is preferably an alkylene monoalkyl ether.
- the hydrophilic organic compound which is an end-capping agent at one end of the polycarbodiimide compound (A) is a polyoxyalkylene monoalkyl ether having n of 7 to 30 in the formula (1) and having a molecular weight of 340 or more. It is also preferable that the hydrophilic organic compound which is the end-capping agent at the other end is a polyoxyalkylene monoalkyl ether having an m of less than 7 and a molecular weight of less than 340 in the formula (1).
- the hydrophilic organic compound may be used alone or in combination of two or more. That is, both ends of the polycarbodiimide (A) may be sealed with the same hydrophilic organic compound or may be sealed with different hydrophilic organic compounds. From the viewpoint of ease of production, it is preferably one kind of hydrophilic organic compound.
- the method for producing the polycarbodiimide compound (A) is not particularly limited, and a known production method can be used. For example, a synthesis method as shown in the following (a1) to (a3) can be mentioned.
- a carbodiimidization reaction of a diisocyanate compound (Da) is carried out in the presence of a catalyst to obtain an isocyanate-terminated polycarbodiimide compound, and then a hydrophilic organic compound (terminal sealant) is added to carry out a terminal sealing reaction.
- A2 A method of mixing a diisocyanate compound (Da) and a hydrophilic organic compound (terminal encapsulant) to carry out a carbodiimideization reaction and an end-sealing reaction in the presence of a catalyst (a3) A diisocyanate compound (Da). ) And a hydrophilic organic compound (terminal encapsulant) to carry out a terminal encapsulation reaction of isocyanate groups, and then a carbodiimideization reaction in the presence of a catalyst.
- the method (a1) or (a3) is preferable from the viewpoint of controlling the degree and manufacturing efficiency.
- the diisocyanate compound (Da) used for producing the polycarbodiimide compound (A) is not particularly limited, and may be any of a chain or alicyclic aliphatic diisocyanate compound, an aromatic diisocyanate compound, or a heterocyclic diisocyanate compound. Often, these may be used alone or in combination of two or more. Examples of the chain aliphatic diisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
- Examples of the aliphatic cyclic diisocyanate compound include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 2,2-bis (4-isocyanatocyclohexyl) propane, and isophorone diisocyanate. Examples thereof include dicyclohexylmethane-4,4'-diisocyanate.
- Examples of the aromatic diisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, 2,4,6-triisopropylbenzene-1,3-diyldiisocyanate and the like.
- the aliphatic diisocyanate compound containing an aromatic ring examples include xylylene diisocyanate and 1,3-bis (2-isocyanato-2-propyl) benzene (common name: tetramethylxylylene diisocyanate).
- the diisocyanate compound (Da) is preferably a diisocyanate compound having an alicyclic or an aromatic ring from the viewpoint of easy availability, good storage stability of the aqueous resin cross-linking agent, and the like.
- dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and tetramethylxylylene diisocyanate are preferable, and tetramethylxylylene diisocyanate and dicyclohexylmethane-4,4'-diisocyanate are preferable. More preferred. In particular, dicyclohexylmethane-4,4'-diisocyanate is preferable.
- the carbodiimidization reaction is preferably, for example, polymerization (decarboxylation condensation reaction) of the diisocyanate compound (Da) in the presence of a carbodiimidization catalyst (US Pat. No. 2,491956, JP-A-47-33279). , J. Org. Chem. 28, p.2069-2075 (1963), Chemical Review 1981, Vol.81, No.4, p.619-621, etc.).
- Examples of the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and 3 -Methyl-2-phospholene-1-oxide and phosphorene oxides such as these 3-phosphoren isomers can be mentioned. Among these, 3-methyl-1-phenyl-2-phospholene-1-oxide is preferable from the viewpoint of reactivity and availability.
- the amount of the carbodiimidization catalyst used is usually preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and further preferably 0 with respect to 100 parts by mass of the diisocyanate compound (Da). .07 to 3 parts by mass.
- the decarboxylation condensation reaction of the diisocyanate compound can be carried out with or without a solvent.
- the solvent used include alicyclic ethers such as tetrahydrofuran, 1,3-dioxane and dioxolan; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; chlorobenzene, dichlorobenzene, trichlorobenzene, perklen and trichloroethane. , Hydrocarbons such as dichloroethane; cyclohexanone and the like. These may be used alone or in combination of two or more.
- the concentration of the diisocyanate compound (Da) is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, from the viewpoint of homogenization of the reaction system.
- the reaction temperature of the decarboxylation condensation reaction is appropriately set according to the appropriate reaction promotion, the degree of polymerization of the carbodiimide group, and the like. Usually, it is preferably 40 to 250 ° C, more preferably 90 to 230 ° C, and even more preferably 100 to 200 ° C. When the reaction is carried out in a solvent, the temperature is preferably in the range of 40 ° C. to the boiling point of the solvent.
- the reaction time is appropriately set according to the reaction temperature, the degree of polymerization of the carbodiimide group, and the like. Usually, it is preferably 0.5 to 100 hours, more preferably 1 to 70 hours, still more preferably 2 to 30 hours. Further, it is preferable to carry out the reaction in an atmosphere of an inert gas such as nitrogen gas or noble gas.
- the degree of polymerization of the carbodiimide group is not particularly limited, but is preferably 2 to 20, more preferably 2 to 20 from the viewpoint of suppressing gelation of the aqueous resin cross-linking agent in the aqueous medium. It is 3 to 15, more preferably 5 to 7.
- the "degree of polymerization of carbodiimide groups" in the present specification means the number of carbodiimide groups produced by the carbodiimideization reaction.
- the terminal sealing reaction can be carried out, for example, by heating the isocyanate-terminated polycarbodiimide compound and the hydrophilic organic compound (terminal sealing agent) in the method (a1).
- the reaction temperature of the end-sealing reaction is appropriately set within a range in which the side reaction can be suppressed and the reaction can be promoted. Usually, it is preferably 50 to 250 ° C, more preferably 90 to 220 ° C, and even more preferably 130 to 200 ° C.
- the reaction time is appropriately set within a range in which the reaction temperature and side reactions can be suppressed. Usually, it is preferably 0.1 to 20 hours, more preferably 0.5 to 10 hours, still more preferably 0.5 to 5 hours.
- the isocyanate-terminated polycarbodiimide compound is heated to 50 to 200 ° C., preferably 100 to 180 ° C., then a hydrophilic organic compound is added, and the reaction is carried out at 80 to 200 ° C. for 0.5 to 5 hours to poly.
- the carbodiimide compound (A) can be obtained.
- the polycarbodiimide compound (B) is a polycarbodiimide compound having a diisocyanate compound (Db) having one cyclohexyl ring or one benzene ring as a structural unit, and is sealed with an organic compound having isocyanate groups at both ends having a molecular weight of 300 or less. Has a stopped structure.
- the diisocyanate compound (Db) which is a structural unit of the polycarbodiimide compound (B), has one cyclohexyl ring or one benzene ring. Therefore, the polycarbodiimide compound (B) has a molecular skeleton structure in which one cyclohexyl ring or benzene ring (hereinafter, also simply referred to as “ring”) and one carbodiimide group are alternately arranged. Intramolecular rings tend to make polycarbodiimide compounds harder than chain hydrocarbons.
- the polycarbodiimide compound (B) improves the hardness of the cured product of the aqueous resin by the presence of such a ring and the carbodiimide group serving as a cross-linking point with respect to the aqueous resin appropriately dispersed in the molecule. It is presumed that it can contribute to.
- a diisocyanate compound having two or more rings for example, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, naphthyl isocyanate, etc.
- diisocyanate compound (Db) examples include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, tolylene diisocyanate, and 2,4,6-triisopropyl.
- examples thereof include benzene-1,3-diyldiisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. These may be used alone or in combination of two or more.
- the diisocyanate compound (Db) is preferably a compound having a primary isocyanate group from the viewpoint of the ease of reaction of the carbodiimide group of the polycarbodiimide compound (B) with the aqueous resin as a cross-linking point. .. Specifically, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, xylylene diisocyanate and the like are preferable, and isophorone diisocyanate and xylylene diisocyanate are more preferable. be. In particular, isophorone diisocyanate is preferable.
- the polycarbodiimide compound (B) has a structure in which the isocyanate groups at both ends are sealed with an organic compound having a molecular weight of 300 or less. That is, the organic compound having a molecular weight of 300 or less is an end-capping agent at both ends of the polycarbodiimide compound (B).
- the molecular weight of the organic compound used as the terminal encapsulant is more than 300, the concentration of the carbodiimide group as a cross-linking point with respect to the aqueous resin becomes low in the molecule of the polycarbodiimide compound (B), and a good cross-linking action is performed.
- the effect of improving the cross-linking performance such as the hardness and solvent resistance of the cured product of the aqueous resin cannot be sufficiently obtained.
- the organic compound is a terminal encapsulant for an isocyanate group in the polycarbodiimide compound (B), and is not particularly limited as long as it has a molecular weight of 300 or less. It is preferably a compound having an individual.
- the functional group is the same as that of the hydrophilic organic compound, and examples thereof include a hydroxyl group, a primary amino group, a secondary amino group, an epoxy group, an isocyanate group, and a carboxy group.
- the polycarbodiimide compound (B) is a more hydrophobic polycarbodiimide compound having a lower hydrophilicity than the polycarbodiimide compound (A), and the organic compound has one functional group that reacts with an isocyanate group. It is preferable that it does not have a hydrophilic group other than a functional group.
- the organic compound is preferably a compound selected from primary or secondary monoamines, monoisocyanates, monools, monoepoxides and monocarboxylic acids.
- Examples of the primary or secondary monoamine include compounds in which a hydrocarbon group having 1 to 18 carbon atoms is bonded to a nitrogen atom of an amino group.
- Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group and an allyl group.
- Examples thereof include a group, a phenyl group, a methylphenyl group, an ethylphenyl group, a propylphenyl group, a naphthyl group, a benzyl group and the like.
- Specific examples of the monoamine include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, adamantanamine, allylamine, aniline and diphenylamine. And so on. Of these, cyclohexylamine is preferable.
- Examples of the monool include a compound in which a hydrocarbon group having 1 to 18 carbon atoms is bonded to a hydroxyl group.
- the hydrocarbon group is the same as for the monoamine.
- Specific examples of the monool include isopropanol, n-octanol, benzyl alcohol and the like.
- examples of the monoisocyanate include compounds in which a hydrocarbon group having 1 to 18 carbon atoms is bonded to an isocyanate group.
- the hydrocarbon group is the same as for the monoamine.
- Specific examples of the monoisocyanate include butyl isocyanate, pentyl isocyanate, hexyl isocyanate, octyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate, 1-adamantyl isocyanate, benzyl isocyanate, 2-phenylethyl isocyanate, diisopropylphenylisocyanate and the like. Of these, cyclohexyl isocyanate is preferable.
- Examples of the monoepoxide include compounds in which a hydrocarbon group having 1 to 18 carbon atoms is bonded to an epoxy group.
- the hydrocarbon group is the same as for the monoamine.
- Specific examples of the monoepoxide include 1,2-epoxyheptane, 1,2-epoxyhexane, 1,2-epoxydecane, 1,2-epoxy-5-hexene and the like.
- Examples of the monocarboxylic acid include compounds in which a hydrocarbon group having 1 to 18 carbon atoms is bonded to the carboxylic acid.
- the hydrocarbon group is the same as for the monoamine.
- Specific examples of the monocarboxylic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, cyclohexanecarboxylic acid, adamantanacetic acid, phenylacetic acid, benzoic acid and the like. Can be mentioned.
- a hydrophilic organic compound represented by any of the above formulas (1) to (5) and having a molecular weight of 300 or less can also be used.
- these hydrophilic organic compounds the polyoxyalkylene monoalkyl ether represented by the formula (1), the dialkylaminoalcohol represented by the formula (3), or the hydroxycarboxylate alkyl represented by the formula (4).
- Esters are preferable, and for example, polyethylene glycol monomethyl ether, N, N-diethylisopropanolamine, methyl glycolate and the like are preferably used.
- the organic compound may be used alone or in combination of two or more. That is, both ends of the polycarbodiimide (B) may be sealed with the same organic compound or may be sealed with different organic compounds. From the viewpoint of ease of production, it is preferably one kind of organic compound.
- the method for producing the polycarbodiimide compound (B) is not particularly limited, and a known production method can be used. For example, a synthesis method as shown in the following (b1) to (b3) can be mentioned.
- (B1) The diisocyanate compound (Db) is subjected to a carbodiimideization reaction in the presence of a catalyst to obtain an isocyanate-terminated polycarbodiimide compound, and then an organic compound (end-capping agent) is added to carry out a terminal-sealing reaction.
- Method (b2) A method of mixing a diisocyanate compound (Db) and an organic compound (terminal encapsulant) to carry out a carbodiimidization reaction and an end-sealing reaction in the presence of a catalyst (b3) Diisocyanate compound (Db) and an organic compound.
- a method of carrying out a carbodiimidization reaction in the presence of a catalyst after carrying out a terminal sealing reaction of an isocyanate group by reacting with (terminal encapsulant) Among these synthetic methods, control of the degree of polymerization of the carbodiimide group and production efficiency. From the viewpoint of the above, the method (b2) or (b3) is preferable.
- the carbodiimideization reaction and the terminal sealing reaction can be carried out in the same manner as the method for synthesizing the polycarbodiimide compound (A). Since the reactivity differs depending on the type of the raw material compound, the reaction conditions are appropriately adjusted according to the type of the raw material compound.
- the degree of polymerization of the carbodiimide group is not particularly limited, but from the viewpoint of good storage stability when the aqueous resin cross-linking agent coexists with the aqueous medium or the aqueous resin, the degree of polymerization is not particularly limited. It is preferably 2 to 20, more preferably 3 to 15, and even more preferably 5 to 7.
- the content of the polycarbodiimide compound (A) in a total of 100 parts by mass of the polycarbodiimide compound (A) and the polycarbodiimide compound (B) is 5 to 90 parts by mass, preferably 15 to 90 parts by mass in the aqueous resin cross-linking agent. It is 85 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 30 to 70 parts by mass.
- the polycarbodiimide compound (A) is a highly hydrophilic polycarbodiimide compound, and the polycarbodiimide compound (B) is a less hydrophilic and more hydrophobic polycarbodiimide compound. Therefore, it is considered that the aqueous resin cross-linking agent has a mode in which the polycarbodiimide compound (A) disperses the polycarbodiimide compound (B) in an aqueous medium.
- the polycarbodiimide compound (A) contributes to the affinity with the aqueous medium and acts to facilitate the uniform addition of the aqueous resin cross-linking agent to the aqueous resin, while the polycarbodiimide compound (B) is the aqueous resin. On the other hand, it can exhibit a stronger cross-linking action than the polycarbodiimide compound (A). Therefore, it is presumed that the aqueous resin cross-linking agent can improve the hardness and solvent resistance of the cured product of the aqueous resin.
- the content of the polycarbodiimide compound (A) in a total of 100 parts by mass of the polycarbodiimide compound (A) and the polycarbodiimide compound (B) is less than 5 parts by mass, the affinity of the aqueous resin cross-linking agent with the aqueous medium becomes high. Insufficient, good storage stability cannot be obtained when coexisting with an aqueous medium or an aqueous resin, and the cross-linking action on the aqueous resin is not sufficiently exhibited.
- the affinity of the aqueous resin cross-linking agent with the aqueous medium is too large, and when coexisting with the aqueous medium or the aqueous resin, the viscosity increases or gelation occurs. It becomes easy and good storage stability cannot be obtained. Further, also in this case, the cross-linking action on the aqueous resin is not sufficiently exhibited.
- the aqueous resin cross-linking agent may be a solvent, for example, an antioxidant, an ultraviolet absorber, an antifoaming agent, etc., as long as the effects of the present invention are not impaired. May contain the additive of.
- the total content of the polycarbodiimide compound (A) and the polycarbodiimide compound (B) in the aqueous resin cross-linking agent is preferably 85 from the viewpoint of sufficiently exerting the cross-linking action of the aqueous resin cross-linking agent. It is by mass% or more, more preferably 90% by mass or more, still more preferably 95% by mass or more.
- the aqueous resin cross-linking agent can be produced by stirring and mixing the polycarbodiimide compound (A), the polycarbodiimide compound (B), and, if necessary, additives of other components. Further, an aqueous medium may be used at the time of mixing these, and the aqueous resin cross-linking agent may be produced in advance as an aqueous resin cross-linking agent-containing liquid described later.
- the method of stirring and mixing for obtaining the aqueous resin cross-linking agent is not particularly limited, and can be carried out by a known method using, for example, a rotating vane or a magnetic stirrer.
- Conditions such as temperature and time at the time of mixing differ depending on the types of the polycarbodiimide compound (A) and the polycarbodiimide compound (B), but from the viewpoint of efficient and uniform mixing, for example, 1 to 200 ° C. It is preferable to mix for 48 hours.
- the aqueous resin cross-linking agent-containing liquid of the present invention contains the aqueous resin cross-linking agent and the aqueous medium. By preserving the aqueous resin cross-linking agent as a containing liquid containing the same, it becomes easy to uniformly add and mix the cross-linking aqueous resin with the water-based resin, and the handleability can be improved.
- the concentration of the aqueous resin cross-linking agent in the aqueous resin cross-linking agent-containing liquid is appropriately determined from the viewpoint of handleability when uniformly added and mixed with the aqueous resin, efficiency of the cross-linking reaction, etc., but is 10 to 100 mass. %, More preferably 20 to 80% by mass, still more preferably 30 to 50% by mass.
- aqueous medium a medium capable of uniformly dissolving or dispersing each component in the aqueous resin cross-linking agent is used, and a hydrophilic solvent among water, alcohols, ethers, ketones, esters and the like is used. Can be mentioned. These may be used alone or in combination of two or more. Of these, water or a mixed solvent of water and a hydrophilic solvent is preferable, and from the viewpoint of environmental consideration and cost, only water is preferable.
- alcohols include methanol, isopropanol, n-butanol, 2-ethylhexyl alcohol, ethylene glycol, propylene glycol and the like.
- ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, propylene glycol monoethyl ether, 3-methoxy-3-methylbutanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tetrahydrofuran and the like.
- ketones include methyl isobutyl ketone, cyclohexanone, isophorone, acetylacetone and the like.
- esters include ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate.
- the aqueous resin cross-linking agent-containing liquid may contain a surfactant.
- the surfactant By using the surfactant, the polycarbodiimide compound (A) and the polycarbodiimide compound (B) can be uniformly dissolved or dispersed in an aqueous medium, and the storage stability of the aqueous resin cross-linking agent-containing liquid can be further improved.
- the surfactant can also contribute to improving the hardness and solvent resistance of the cured product of the aqueous resin.
- the content thereof is the effect of sufficiently improving the storage stability of the aqueous resin cross-linking agent-containing liquid and the aqueous resin composition using the same, and the curing of the aqueous resin.
- it is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the total of the polycarbodiimide compound (A) and the polycarbodiimide compound (B). It is 0.2 to 10 parts by mass, more preferably 0.3 to 8 parts by mass.
- an anionic surfactant or a nonionic surfactant may be used from the viewpoint of storage stability of the aqueous resin cross-linking agent-containing liquid and the aqueous resin composition using the same, and compatibility with the aqueous resin.
- an anionic surfactant is used.
- One of these may be used alone or two or more thereof may be used in combination.
- anionic surfactant examples include an alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate, an alkyl sulfate such as sodium dodecyl sulfate and sodium lauryl sulfate, sodium N-cocoylmethyl taurine, and sodium di-2-ethylhexyl sulfosuccinate. , Sodium sulphate-2-ethylhexyl, ⁇ -sulfo fatty acid methyl ester sodium salt and the like. Of these, sodium dodecylbenzene sulfonate is preferably used from the viewpoint of availability and the like.
- nonionic surfactant examples include polyoxyethylene-2-ethylhexyl ether, polyethylene glycol monomethyl ether, polyoxyethylene isodecyl ether and the like.
- the molecular weight of these nonionic surfactants is preferably 100 to 2000, more preferably 100 to 1000, still more preferably 300 to 1000, from the viewpoint of ease of addition and mixing.
- the aqueous resin cross-linking agent-containing liquid contains the above-mentioned water-based resin cross-linking agent, an aqueous medium, and a surfactant added as necessary, and is aqueous as an optional component other than these as long as the effect of the present invention is not impaired.
- a solvent and an additive such as an antioxidant, an ultraviolet absorber, an antioxidant, and an antifoaming agent may be further added.
- the aqueous resin cross-linking agent-containing liquid can be produced by mixing the aqueous resin cross-linking agent, the aqueous medium, and if necessary, a surfactant, and additives of other components.
- the method of stirring and mixing is not particularly limited, and for example, a known method using a rotary blade, a magnetic stirrer, or the like can be used.
- Conditions such as temperature and time at the time of mixing differ depending on the composition of the aqueous resin cross-linking agent, the type of the aqueous medium, etc., but from the viewpoint of efficient and uniform mixing, for example, the aqueous resin cross-linking agent and the aqueous medium are mixed. In some cases, it is preferable to stir and mix at 20 to 100 ° C. for 0.5 to 5 hours.
- the aqueous resin composition of the present invention contains the aqueous resin cross-linking agent and the aqueous resin. Since the above-mentioned aqueous resin cross-linking agent of the present invention has excellent storage stability in the state of coexisting with the aqueous resin, the aqueous resin composition can be used for a long period of time after production, even after at least one week has passed. The cross-linking reaction can be satisfactorily carried out by heating or the like. Further, by using the aqueous resin composition, a cured product of the aqueous resin having high hardness of the coating film and good solvent resistance can be obtained.
- the aqueous resin is a resin having water solubility or water dispersibility.
- the aqueous resin can be crosslinked by an aqueous resin crosslinking agent, and is particularly preferably one having a crosslinkable group that can be crosslinked by a carbodiimide group.
- the aqueous resin preferably has a functional group selected from a carboxy group, an amino group and a hydroxyl group as a crosslinkable group, and has an alcoholic hydroxyl group and / or a carboxy group. Is more preferable.
- water-based resin examples include polyester resin, acrylic resin, polyurethane resin, epoxy resin, styrene-acrylic resin, melamine resin, polyolefin resin, fluororesin and the like, which are water-based resins having such crosslinkable groups. .. These may be used alone or in combination of two or more. Of these, polyester resin, acrylic resin, and polyurethane resin are particularly preferably used.
- the content of the aqueous resin cross-linking agent in the aqueous resin composition is appropriately determined according to the type of the aqueous resin, the physical characteristics required for the cured product of the aqueous resin, etc., but from the viewpoint of the balance between the cross-linking reactivity and the cost, etc.
- the amount is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, and further preferably 1.5 to 20 parts by mass with respect to 100 parts by mass of the aqueous resin.
- the aqueous resin composition may contain other components as long as the effects of the present invention are not impaired. Specifically, apart from the solvent and additives in the aqueous resin cross-linking agent or the aqueous resin cross-linking agent-containing liquid, a solvent, for example, a colorant, a filler, a dispersion, if necessary, depending on the purpose of use, application, etc. Various additives such as agents, plasticizers, thickeners, ultraviolet absorbers, and antioxidants may be further added.
- the aqueous resin composition can be produced by adding the aqueous resin cross-linking agent, the aqueous resin, the other components and the like in any order, and stirring and mixing them.
- the method of stirring and mixing is not particularly limited, and for example, a known method using a rotary blade, a magnetic stirrer, or the like can be used.
- Conditions such as temperature and time at the time of mixing differ depending on the composition of the aqueous resin cross-linking agent, the type of the aqueous resin, and the like, but from the viewpoint of efficient and uniform mixing, the mixing temperature is preferably 0 to 100 ° C. More preferably, it is 10 to 50 ° C.
- the temperature is more preferably 20 to 30 ° C.
- the mixing time is preferably 0.1 to 2 hours, more preferably 0.3 to 1 hour.
- the aqueous resin composition may be produced by mixing with the aqueous resin as the above-mentioned aqueous resin cross-linking agent-containing liquid from the viewpoint of uniform mixing with the aqueous resin and ease of handling. ..
- the aqueous resin composition undergoes a cross-linking reaction by heating or the like to produce a cured product of the aqueous resin (aqueous resin composition).
- the cured product can be formed as a cured film by applying the aqueous resin composition on a predetermined substrate and then heating the cured product to cause a cross-linking reaction.
- a known method can be used, for example, brush coating, tampo coating, spray coating, hot spray coating, airless spray coating, roller coating, curtain flow coating, sink coating, and dipping coating. , Knife fedge coat, etc. can be adopted.
- the heating method is not particularly limited, and for example, an electric heating furnace, an infrared heating furnace, a high frequency heating furnace, or the like can be used.
- the heating temperature is appropriately set from the viewpoint of promoting the crosslinking reaction within a range in which the aqueous resin composition is not discolored or thermally decomposed according to the composition of the aqueous resin crosslinking agent, the type of the aqueous resin, and the like.
- the water-based resin composition can be used, for example, as a paint, an ink, or a fiber treatment agent.
- a cured film (coating film) of an aqueous resin having high hardness and excellent solvent resistance can be obtained, and such a cured film can be formed on an arbitrary substrate. You can also get the formed article.
- the base material may be any material such as metal, ceramics, resin, wood, cloth, fiber, etc., regardless of whether it is an inorganic material or an organic material.
- the aqueous resin composition can be suitably applied to wet-on-wet coating.
- the coating film formed of the aqueous resin composition is highly resistant to bleeding and poor adhesion between the laminated coating films by promoting the cross-linking reaction. A cured film having good hardness and good interlayer adhesion can be efficiently formed.
- the aqueous resin composition can also exhibit various physical properties based on other excellent crosslinkability.
- an article in which the cured film is formed on a substrate has high tensile strength and high tensile strength. It can also be applied to applications that require excellent heat resistance, durability, adhesiveness, adhesion, chipping resistance, scratch resistance and compatibility. Specifically, it can be suitably applied in the fields of automobiles, construction, heavy-duty anticorrosion coating, food packaging, healthcare and the like.
- ⁇ Terminal sealant> -MP550 Polyethylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 525-575) -MP208: Tetraethylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 208.25) -CHI: Cyclohexyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 125.17) C8: n-octanol (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 130.23) -BzOH: Benzyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 108.14) -IPA: Isopropanol (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 60.10) -GM: Methyl glycolate (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight
- a toluene solution of di-n-butylamine having a known concentration is mixed with the isocyanate-terminated polycarbodiimide obtained by the carbodiimideization reaction, and the terminal isocyanate group is reacted with di-n-butylamine to remain.
- Di-n-butylamine was neutralized and titrated with a hydrochloric acid standard solution, and the residual amount of isocyanate groups (terminal NCO amount [mass%]) was calculated. From this amount of terminal NCO, the degree of polymerization of the carbodiimide group was determined.
- aqueous resin cross-linking agent-containing liquid was prepared using each of the polycarbodiimide compounds obtained in the above synthetic example.
- the details of the surfactant used in the following Examples and Comparative Examples are as follows. ⁇ Surfactant> ⁇ C1: Sodium dodecylbenzene sulfonate, anionic ⁇ C2: Sodium N-cocoylmethyl taurine, anionic ⁇ C3: Sodium lauryl sulfate, anionic ⁇ C4: Polyoxyethylene-2-ethylhexyl ether, nonionic
- Examples 1 to 3 and 8 to 28, Comparative Examples 1 to 5 The polycarbodiimide compound (A) and the polycarbodiimide compound (B) are stirred and mixed at 160 ° C. for 4 hours at 160 ° C. with each type and blending amount shown in Table 1 below, cooled to 80 ° C., and 150 parts by mass of ion-exchanged water. Diluted with, and stirred and mixed to obtain each aqueous resin cross-linking agent-containing liquid.
- Examples 4 to 7 40 parts by mass of the polycarbodiimide compound (A) and 60 parts by mass of the polycarbodiimide compound (B) of each type shown in Table 1 below are stirred and mixed at 160 ° C. for 4 hours, cooled to 80 ° C., and an aqueous solution of the surfactant. 3 parts by mass (in terms of active ingredient) was added, diluted with 150 parts by mass of ion-exchanged water, and stirred and mixed to obtain each aqueous resin cross-linking agent-containing liquid.
- shelf life (storage stability) of each of the aqueous resin cross-linking agent-containing liquids obtained in the above Examples and Comparative Examples was evaluated as follows. The evaluation results are shown in Table 2 below.
- Shelf life (storage stability)
- the shelf life (storage stability) was evaluated by determining the rate of change in viscosity after 90 days of storage with respect to the viscosity immediately after production.
- the viscosity was measured with a B-type viscometer (“TVB-10M”, manufactured by Toki Sangyo Co., Ltd .; rotor: TM2, sample volume 50 mL, temperature 20 ° C., rotation speed 60 rpm).
- the viscosity change rate was evaluated according to the following evaluation criteria. The closer the viscosity change rate is to 0%, the better the storage stability is, and in the case of evaluations AA to C, it can be said that the storage stability is good.
- the evaluation results are shown in Table 1 below.
- AA Viscosity change rate less than 5%
- B Viscosity change rate 10% or more and less than 20%
- C Viscosity change rate 20% or more and less than 30%
- D Viscosity change rate 30% or more 50 Less than%
- E Viscosity change rate 50% or more
- aqueous resin composition 5 parts by mass of the cross-linking agent-containing liquid for each aqueous resin (2 parts by mass as the cross-linking agent) produced in the above Examples and Comparative Examples, and a carboxy group-containing aqueous polyurethane resin (“Hydran (registered trademark) WLS-210”, DIC stock Aqueous polyurethane resin composition was prepared by stirring and mixing with 285 parts by mass (100 parts by mass of resin solid content) manufactured by the company (resin solid content 35% by mass).
- Aqueous polyester resin composition 5 parts by mass of the cross-linking agent-containing liquid for each aqueous resin (2 parts by mass as the cross-linking agent) produced in the above Examples and Comparative Examples and a carboxy group-modified aqueous polyester resin (“Plus Coat (registered trademark) Z-730”, interchangeable 400 parts by mass (100 parts by mass of resin solid content) (manufactured by Kagaku Kogyo Co., Ltd., resin solid content 25% by mass) was stirred and mixed to prepare an aqueous polyester resin composition.
- Plus Coat registered trademark
- Z-730 interchangeable 400 parts by mass (100 parts by mass of resin solid content)
- Viscosity change rate less than 10%
- A Viscosity change rate 10% or more and less than 20%
- B Viscosity change rate 20% or more and less than 30%
- C Viscosity change rate 30% or more and less than 50%
- D Viscosity change rate 50% or more 100 Less than%
- E Viscosity change rate 100% or more
- the aqueous resin composition was applied onto a release polyethylene terephthalate (PET) film using a bar coater (wire rod No. 32), dried at 80 ° C. for 10 minutes, and then dried at room temperature (25 ° C.) for 1 day. It was left to form a coating film.
- the coating film peeled from the release PET film was used as a coating film test piece.
- the tensile test and the pencil hardness test shown below were performed on the coating film test piece, and the coating film hardness was evaluated by integrating these test results.
- the score was evaluated according to the standard, and the average score for 10 coating film test pieces was obtained and used as the evaluation score.
- Pencil hardness test According to JIS K 5600-5-4: 1999, the pencil hardness was measured for 10 points of the coating film test piece using a pencil hardness tester. The measured pencil hardness was scored according to the following score criteria, and the average score for 10 coating film test pieces was obtained and used as an evaluation score.
- the aqueous resin composition was applied onto an aluminum plate using a bar coater (wire rod No. 32) and dried at 80 ° C. for 10 minutes to obtain a coating film test piece.
- the coating film test piece is double-rubbed 50 times with a friction tester (“FR-1B”, manufactured by Suga Test Instruments Co., Ltd.) using absorbent cotton (load 900 g / cm 2 ) impregnated with a 70 mass% ethanol aqueous solution.
- a friction test was performed. Visually observe the coating film test piece after the friction test, score each evaluation item of whitening property and coating film residual area ratio according to the following score criteria, and obtain the average score for the two coating film test pieces. Was used as the evaluation point.
- the aqueous resin cross-linking agent of the present invention has excellent storage stability of the content liquid prepared by using the aqueous resin cross-linking agent, and when coexistent with the aqueous resin (aqueous resin composition). It was found that the storage stability of the product) was excellent, and that the hardness and solvent resistance of the coating film could be improved for the cured products of various aqueous resins. It was also found that even in wet-on-wet coating, a cured film with a multi-layer coating film having good interlayer adhesion can be formed.
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Abstract
Description
このため、水性樹脂の耐水性や耐久性、強度等の諸物性を向上させるために、該水性樹脂には、架橋剤が添加される。
[1]ポリカルボジイミド化合物(A)及びポリカルボジイミド化合物(B)を含有し、前記ポリカルボジイミド化合物(A)は、両末端のイソシアネート基がそれぞれ親水性有機化合物で封止された構造であり、前記親水性有機化合物の少なくとも一方が分子量340以上であり、前記ポリカルボジイミド化合物(B)は、シクロヘキシル環1個又はベンゼン環1個を有するジイソシアネート化合物を構造単位とし、両末端のイソシアネート基がそれぞれ分子量300以下の有機化合物で封止された構造であり、前記ポリカルボジイミド化合物(A)及び前記ポリカルボジイミド化合物(B)の合計100質量部中の前記ポリカルボジイミド化合物(A)が5~90質量部である、水性樹脂架橋剤。
[2]分子量340以上の前記親水性有機化合物が、下記式(1)で表される化合物である、上記[1]に記載の水性樹脂架橋剤。
R1(OCHR2CH2)nOH (1)
(式(1)中、R1は、炭素数1~20の、アルキル基、シクロアルキル基又はアリール基である。R2は、水素原子又はメチル基である。nは7~30の数である。)
[3]前記式(1)中、R1がメチル基であり、R2が水素原子である、上記[2]に記載の水性樹脂架橋剤。
[4]分子量300以下の前記有機化合物が、イソシアネート基と反応する官能基を1個有する化合物である、上記[1]~[3]のいずれかに記載のカルボジイミド系水性樹脂架橋剤。
[5]分子量300以下の前記有機化合物が、第一級又は第二級のモノアミン、モノイソシアネート、モノオール、モノエポキシド及びモノカルボン酸から選ばれる化合物である、上記[1]~[4]のいずれか1項に記載の水性樹脂架橋剤。
[6]前記ジイソシアネート化合物が、第一級イソシアネート基を有する化合物である、上記[1]~[5]のいずれか1項に記載の水性樹脂架橋剤。
[8]前記水性媒体が、水、又は水と親水性溶媒との混合溶媒である、上記[7]に記載の水性樹脂架橋剤含有液。
[9]さらに界面活性剤を含有する、上記[7]又は[8]に記載の水性樹脂架橋剤含有液。
[10]前記界面活性剤が、アニオン性界面活性剤である、上記[9]に記載の水性樹脂用架橋剤含有液。
[11]前記アニオン性界面活性剤が、アルキルベンゼンスルホン酸塩、アルキル硫酸塩、及びN-ココイルメチルタウリンナトリウムから選ばれる1種以上である、上記[10]に記載の水性樹脂用架橋剤含有液。
[13]前記水性樹脂が、カルボキシ基、アミノ基及び水酸基から選ばれる官能基を有する、上記[12]に記載の水性樹脂組成物。
[14]前記水性樹脂が、ポリエステル樹脂、アクリル樹脂、ポリウレタン樹脂、エポキシ樹脂、スチレン-アクリル樹脂、メラミン樹脂、ポリオレフィン樹脂及びフッ素樹脂から選ばれる1種以上である、上記[12]又は[13]に記載の水性樹脂組成物。
[15]接着剤、繊維処理剤、コーティング剤、インキ、塗料又は粘着剤に用いられる、上記[12]~[14]のいずれか1項に記載の水性樹脂組成物。
[16]ウェット・オン・ウェット方式の塗装用である、上記[12]~[14]のいずれか1項に記載の水性樹脂組成物。
[17]上記[12]~[16]のいずれか1項に記載の水性樹脂組成物により形成された硬化膜。
[18]上記[17]に記載の硬化膜が、基材上に形成されてなる物品。
したがって、前記水性樹脂架橋剤を含む水性樹脂組成物は、接着剤や繊維処理剤、コーティング剤、インキ、塗料、粘着剤等の用途に好適に用いることができる。
なお、本発明で言う「水性」とは、水性媒体に対する溶解性又は分散性を有していることを意味する。「水性媒体」とは、水及び/又は親水性溶媒を指すものとする。また、「ポリカルボジイミド化合物」とは、2個以上のカルボジイミド基を有する化合物を指す。
本発明の水性樹脂架橋剤は、ポリカルボジイミド化合物(A)及びポリカルボジイミド化合物(B)を含有し、両者の合計100質量部中のポリカルボジイミド化合物(A)が5~90質量部であることを特徴とする。すなわち、前記水性樹脂架橋剤は、(A)及び(B)の2種のポリカルボジイミド化合物を含むものである。
このような配合組成からなる水性樹脂架橋剤は、水性媒体中での保存安定性に優れ、また、水性樹脂と併存させた場合の保存安定性にも優れ、水性樹脂の硬化物について、塗膜の硬度及び耐溶剤性を向上させることができる。
ポリカルボジイミド化合物(A)は、両末端のイソシアネート基がそれぞれ親水性有機化合物で封止された構造のポリカルボジイミド化合物であり、前記親水性有機化合物の少なくとも一方が分子量340以上である。
前記親水性有機化合物は、イソシアネート基と反応性を有する官能基を1個以上有し、かつ、該官能基以外の構造中にヘテロ原子を1個以上有する化合物であることが好ましい。前記官能基としては、水酸基、第一級アミノ基、第二級アミノ基、エポキシ基、イソシアネート基、及びカルボキシ基等が挙げられる。すなわち、前記親水性有機化合物は、水酸基、第一級アミノ基、第二級アミノ基、エポキシ基、イソシアネート基、及びカルボキシ基から選ばれるいずれかの官能基を有し、かつ、該官能基以外の構造中にヘテロ原子を1個以上有する化合物であることがより好ましい。
R1(OCHR2CH2)nOH (1)
R2は水素原子又はメチル基である。
R1はメチル基であることがより好ましく、また、R2は水素原子であることがより好ましい。
nは1~30の数であり、ポリカルボジイミド化合物(A)の良好な親水性の観点から、好ましくは7~30、より好ましくは8~20である。
なお、式(1)で表される化合物は、オキシアルキレン基(OCHR2CH2)の数が異なる分子の集合体である場合もある。この場合は、各分子中のオキシアルキレン基の数の平均値をnとする。
HOR3SO3M (2)
Mはアルカリ金属原子であり、好ましくは、Na又はKである。
R4 2NCH2CHR5OH (3)
R5は水素原子又は炭素数1~4のアルキル基である。アルキル基は、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、s-ブチル基、イソブチル基、及びt-ブチル基が挙げられる。
R6OCOCHR7OH (4)
R7は水素原子又は炭素数1~3のアルキル基であり、アルキル基としては、メチル基、エチル基、プロピル基、及びイソプロピル基が挙げられる。
R8 2-N-R9-NH2 (5)
R9は炭素数1~4のアルキレン基であり、具体的には、メチレン基、エチレン基、プロピレン基、テトラメチレン基等が挙げられる。
R10(OCHR11CH2)nOR12 (6)
R11は水素原子又は炭素数1~4のアルキレン基であり、具体的には、メチレン基、エチレン基、プロピレン基、テトラメチレン基等が挙げられる。
R12は炭素数1~4のアミノアルキル基である。アミノアルキル基としては、具体的には、アミノメチル基、アミノエチル基、アミノプロピル基、アミノイソプロピル基、アミノ-n-ブチル基、アミノ-s-ブチル基、イソアミノブチル基、及びアミノ-t-ブチル基が挙げられる。
親水性有機化合物として、式(1)においてnが7~30であるポリオキシアルキレンモノアルキルエーテルを用いる場合、式(1)においてnが7未満のポリオキシアルキレンモノアルキルエーテル、式(3)で表されるジアルキルアミノアルコール、及び式(4)で表されるヒドロキシカルボン酸アルキルエステルから選ばれる1種以上の化合物と併用することも好ましい。
分子量が340以上の親水性有機化合物としては、式(1)で表される化合物のうちのポリオキシアルキレンモノアルキルエーテルが好ましい。保存安定性の観点から、分子量が450~600のポリオキシアルキレンモノアルキルエーテルがより好ましい。
例えば、ポリカルボジイミド化合物(A)の両末端のいずれについても、末端封止剤である親水性有機化合物が、式(1)においてnが7~30であり、分子量340以上の同一又は異なるポリオキシアルキレンモノアルキルエーテルであることが好ましい。また、ポリカルボジイミド化合物(A)の片末端の末端封止剤である親水性有機化合物が、式(1)においてnが7~30であり、分子量340以上のポリオキシアルキレンモノアルキルエーテルであり、他方の片末端の末端封止剤である親水性有機化合物が、式(1)においてmが7未満であり、分子量340未満のポリオキシアルキレンモノアルキルエーテルであることも好ましい。
ポリカルボジイミド化合物(A)の製造方法は、特に限定されるものではなく、公知の製造方法を用いて行うことができる。例えば、下記(a1)~(a3)に示すような合成方法が挙げられる。
(a1)ジイソシアネート化合物(Da)を触媒の存在下でカルボジイミド化反応させて、イソシアネート末端ポリカルボジイミド化合物を得た後、次いで、親水性有機化合物(末端封止剤)を添加して末端封止反応を行う方法
(a2)ジイソシアネート化合物(Da)及び親水性有機化合物(末端封止剤)を混合して、触媒の存在下でカルボジイミド化反応及び末端封止反応を行う方法
(a3)ジイソシアネート化合物(Da)及び親水性有機化合物(末端封止剤)を反応させてイソシアネート基の末端封止反応を行った後、触媒の存在下でカルボジイミド化反応を行う方法
これらの合成方法のうち、カルボジイミド基の重合度の制御及び製造効率等の観点から、(a1)又は(a3)の方法が好ましい。
鎖状脂肪族ジイソシアネート化合物としては、例えば、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ドデカメチレンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート等が挙げられる。
脂環状ジイソシアネート化合物としては、例えば、1,3-ビス(イソシアナトメチル)シクロヘキサン、1,4-ビス(イソシアナトメチル)シクロヘキサン、2,2-ビス(4-イソシアナトシクロヘキシル)プロパン、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’-ジイソシアネート等が挙げられる。
芳香族ジイソシアネート化合物としては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、2,4,6-トリイソプロピルベンゼン-1,3-ジイルジイソシアネート等が挙げられる。
また、芳香環を含む脂肪族ジイソシアネート化合物としては、例えば、キシリレンジイソシアネート、1,3-ビス(2-イソシアナト-2-プロピル)ベンゼン(慣用名:テトラメチルキシリレンジイソシアネート)等が挙げられる。
これらの中でも、ジイソシアネート化合物(Da)としては、入手容易性、水性樹脂架橋剤の良好な保存安定性等の観点から、脂環又は芳香環を有するジイソシアネート化合物であることが好ましい。具体的には、ジシクロヘキシルメタン-4,4’-ジイソシアネート、イソホロンジイソシアネート、4,4’-ジフェニルメタ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が好ましく、テトラメチルキシリレ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。特に、ジシクロヘキシルメタン-4,4’-ジイソシアネートが好ましい。
前記カルボジイミド化触媒としては、例えば、1-フェニル-2-ホスホレン-1-オキシド、3-メチル-1-フェニル-2-ホスホレン-1-オキシド、1-エチル-2-ホスホレン-1-オキシド、3-メチル-2-ホスホレン-1-オキシド及びこれらの3-ホスホレン異性体等のホスホレンオキシド等が挙げられる。これらの中でも、反応性や入手容易性等の観点から、3-メチル-1-フェニル-2-ホスホレン-1-オキシドが好ましい。
前記カルボジイミド化触媒の使用量は、通常、ジイソシアネート化合物(Da)100質量部に対して0.01~10質量部であることが好ましく、より好ましくは0.05~5質量部、さらに好ましくは0.07~3質量部である。
溶媒中で反応を行う場合、ジイソシアネート化合物(Da)の濃度は、反応系の均一化の観点から、5~80質量%とすることが好ましく、より好ましくは20~60質量%である。
また、反応時間は、反応温度やカルボジイミド基の重合度等に応じて適宜設定される。通常、0.5~100時間であることが好ましく、より好ましくは1~70時間、さらに好ましくは2~30時間である。
また、窒素ガス、希ガス等の不活性ガス雰囲気下で反応を行うことが好ましい。
なお、本明細書における「カルボジイミド基の重合度」とは、前記カルボジイミド化反応により生成したカルボジイミド基の数を言う。
末端封止反応の反応温度は、副反応を抑制し、反応を促進し得る範囲内で適宜設定される。通常、50~250℃であることが好ましく、より好ましくは90~220℃、さらに好ましくは130~200℃である。
また、反応時間は、反応温度や副反応を抑制し得る範囲内で適宜設定される。通常、0.1~20時間であることが好ましく、より好ましくは0.5~10時間、さらに好ましくは0.5~5時間である。
例えば、イソシアネート末端ポリカルボジイミド化合物を、50~200℃、好ましくは100~180℃に加熱した後、親水性有機化合物を添加し、80~200℃で0.5~5時間反応させることにより、ポリカルボジイミド化合物(A)を得ることができる。
ポリカルボジイミド化合物(B)は、シクロヘキシル環1個又はベンゼン環1個を有するジイソシアネート化合物(Db)を構造単位とするポリカルボジイミド化合物であり、両末端のイソシアネート基がそれぞれ分子量300以下の有機化合物で封止された構造を有する。
ポリカルボジイミド化合物(B)の構造単位であるジイソシアネート化合物(Db)は、シクロヘキシル環1個又はベンゼン環1個を有している。
このため、ポリカルボジイミド化合物(B)は、シクロヘキシル環又はベンゼン環(以下、単に「環」とも言う。)1個とカルボジイミド基1個とが交互に並んだ分子骨格構造を有している。分子内の環は、鎖状炭化水素に比べて、ポリカルボジイミド化合物を硬くする傾向がある。このような環と、水性樹脂に対する架橋点となるカルボジイミド基とが、分子内で適度に分散して存在していることにより、ポリカルボジイミド化合物(B)は、水性樹脂の硬化物の硬度の向上に寄与し得るものと推測される。
環を2個以上有するジイソシアネート化合物(例えば、ジシクロヘキシルメタンジイソシアネート、ジフェニルメタンジイソシアネート、ナフチルイソシアネート等)は、環の数が多くても、2個以上の環を含む構造によって、ポリカルボジイミド化合物の分子鎖におけるカルボジイミド基同士の間隔が広がり、却って、水性樹脂の硬化物の硬度を向上させる効果が抑制されるものと推測される。
これらのうち、ポリカルボジイミド化合物(B)のカルボジイミド基の水性樹脂に対する架橋点としての反応しやすさ等の観点から、ジイソシアネート化合物(Db)は、第一級イソシアネート基を有する化合物であることが好ましい。具体的には、1,3-ビス(イソシアナトメチル)シクロヘキサン、1,4-ビス(イソシアナトメチル)シクロヘキサン、イソホロンジイソシアネート、キシリレンジイソシアネート等が好ましく、より好ましくは、イソホロンジイソシアネート、キシリレンジイソシアネートである。特に、イソホロンジイソシアネートが好ましい。
ポリカルボジイミド化合物(B)は、両末端のイソシアネート基がそれぞれ分子量300以下の有機化合物で封止された構造を有している。すなわち、分子量300以下の前記有機化合物は、ポリカルボジイミド化合物(B)の両末端の末端封止剤である。
末端封止剤として用いられる有機化合物の分子量が300超の場合は、ポリカルボジイミド化合物(B)の分子内において、水性樹脂に対して架橋点となるカルボジイミド基の濃度が低くなり、良好な架橋作用が得られず、水性樹脂の硬化物の硬度及び耐溶剤性等の架橋性能を向上させる効果が十分に得られない。
前記官能基としては、前記親水性有機化合物についてと同様であり、水酸基、第一級アミノ基、第二級アミノ基、エポキシ基、イソシアネート基、及びカルボキシ基等が挙げられる。
前記有機化合物としては、第一級又は第二級モノアミン、モノイソシアネート、モノオール、モノエポキシド及びモノカルボン酸から選ばれる化合物であることが好ましい。
前記モノアミンの具体例としては、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、オクチルアミン、ドデシルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、シクロヘキシルアミン、アダマンタンアミン、アリルアミン、アニリン、ジフェニルアミン等が挙げられる。これらのうち、シクロヘキシルアミンが好ましい。
前記モノオールの具体例としては、イソプロパノール、n-オクタノール、ベンジルアルコール等が挙げられる。
前記モノイソシアネートの具体例としては、ブチルイソシアネート、ペンチルイソシアネート、ヘキシルイソシアネート、オクチルイソシアネート、ドデシルイソシアネート、シクロヘキシルイソシアネート、1-アダマンチルイソシアネート、イソシアン酸ベンジル、2-フェニルエチルイソシアネート、ジイソプロピルフェニルイソシアネート等が挙げられる。これらのうち、シクロヘキシルイソシアネートが好ましい。
前記モノエポキシドの具体例としては、1,2-エポキシヘプタン、1,2-エポキシヘキサン、1,2-エポキシデカン、1,2-エポキシ-5-ヘキセン等が挙げられる。
前記モノカルボン酸の具体例としては、酢酸、プロピオン酸、ブタン酸、ペンタン酸、ヘキサン酸、へプタン酸、オクタン酸、ノナン酸、デカン酸、シクロヘキサンカルボン酸、アダマンタン酢酸、フェニル酢酸、安息香酸等が挙げられる。
ポリカルボジイミド化合物(B)の製造方法は、特に限定されるものではなく、公知の製造方法を用いて行うことができる。例えば、下記(b1)~(b3)に示すような合成方法が挙げられる。
(b1)ジイソシアネート化合物(Db)を触媒の存在下でカルボジイミド化反応させて、イソシアネート末端ポリカルボジイミド化合物を得た後、次いで、有機化合物(末端封止剤)を添加して末端封止反応を行う方法
(b2)ジイソシアネート化合物(Db)及び有機化合物(末端封止剤)を混合して、触媒の存在下でカルボジイミド化反応及び末端封止反応を行う方法
(b3)ジイソシアネート化合物(Db)及び有機化合物(末端封止剤)を反応させてイソシアネート基の末端封止反応を行った後、触媒の存在下でカルボジイミド化反応を行う方法
これらの合成方法のうち、カルボジイミド基の重合度の制御及び製造効率等の観点から、(b2)又は(b3)の方法が好ましい。
前記水性樹脂架橋剤は、ポリカルボジイミド化合物(A)及びポリカルボジイミド化合物(B)の合計100質量部中のポリカルボジイミド化合物(A)の含有量が、5~90質量部であり、好ましくは15~85質量部、より好ましくは20~80質量部、さらに好ましくは30~70質量部である。
一方、前記含有量が90質量部超の場合は、水性樹脂架橋剤の水性媒体との親和性が大きすぎて、水性媒体や水性樹脂と併存させた場合に粘度が上昇したり、ゲル化したりしやくなり、良好な保存安定性が得られない。また、この場合も、水性樹脂に対する架橋作用が十分に発揮されない。
前記水性樹脂架橋剤は、ポリカルボジイミド化合物(A)及びポリカルボジイミド化合物(B)以外に、本発明の効果を損なわない範囲において、溶剤や、例えば、酸化防止剤、紫外線吸収剤、消泡剤等の添加剤を含んでいてもよい。この場合、水性樹脂架橋剤による架橋作用が十分に発揮されるようにする観点から、水性樹脂架橋剤中のポリカルボジイミド化合物(A)及びポリカルボジイミド化合物(B)の合計含有量は、好ましくは85質量%以上、より好ましくは90質量%以上、さらに好ましくは95質量%以上である。
水性樹脂架橋剤は、ポリカルボジイミド化合物(A)、ポリカルボジイミド化合物(B)、及び、必要に応じて、その他の成分の添加剤等を撹拌混合することにより、製造することができる。また、これらの混合の際に水性媒体を用い、水性樹脂架橋剤を、予め、後述する水性樹脂架橋剤含有液として製造してもよい。
水性樹脂架橋剤を得るための撹拌混合の方法は、特に限定されるものではなく、例えば、回転羽根やマグネチックスターラー等を用いた公知の方法により行うことができる。
混合時の温度や時間等の条件は、ポリカルボジイミド化合物(A)及びポリカルボジイミド化合物(B)の種類等によって異なるが、効率的に均一に混合する観点から、例えば、60~200℃で1~48時間混合することが好ましい。
本発明の水性樹脂架橋剤含有液は、前記水性樹脂架橋剤及び水性媒体を含むものである。前記水性樹脂架橋剤を、これを含む含有液としておくことにより、架橋する水性樹脂に対して均一に添加混合することが容易となり、取り扱い性に優れたものとすることができる。
水性媒体は、前記水性樹脂架橋剤中の各含有成分を均一に溶解又は分散可能である媒体が用いられ、水や、アルコール類、エーテル類、ケトン類、エステル類等のうちの親水性溶媒が挙げられる。これらは、1種単独で用いても、2種以上を併用してもよい。これらのうち、水、又は水と親水性溶媒との混合溶媒であることが好ましく、環境配慮やコスト等の観点からは、水のみであることが好ましい。
アルコール類としては、例えば、メタノール、イソプロパノール、n-ブタノール、2-エチルヘキシルアルコール、エチレングリコール、プロピレングリコール等が挙げられる。エーテル類としては、例えば、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、プロピレングリコールモノエチルエーテル、3-メトキシ-3-メチルブタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、テトラヒドロフラン等が挙げられる。ケトン類としては、例えば、メチルイソブチルケトン、シクロヘキサノン、イソホロン、アセチルアセトン等が挙げられる。エステル類としては、例えば、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート等が挙げられる。
前記水性樹脂架橋剤含有液には、界面活性剤が含まれていてもよい。界面活性剤を用いることにより、ポリカルボジイミド化合物(A)及びポリカルボジイミド化合物(B)を水性媒体に均一に溶解又は分散し、水性樹脂架橋剤含有液の保存安定性をより向上させることができる。また、界面活性剤は、水性樹脂の硬化物の硬度や耐溶剤性の向上にも寄与し得る。
アニオン性界面活性剤としては、例えば、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、ドデシル硫酸ナトリウムやラウリル硫酸ナトリウム等のアルキル硫酸塩、N-ココイルメチルタウリンナトリウム、ジ-2-エチルヘキシルスルホコハク酸ナトリウム、硫酸ナトリウム-2-エチルヘキシル、α-スルホ脂肪酸メチルエステルナトリウム塩等が挙げられる。これらのうち、入手容易性等の観点から、ドデシルベンゼンスルホン酸ナトリウムが好適に用いられる。
ノニオン性界面活性剤としては、例えば、ポリオキシエチレン-2-エチルヘキシルエーテル、ポリエチレングリコールモノメチルエーテル、ポリオキシエチレンイソデシルエーテル等が挙げられる。これらのノニオン性界面活性剤の分子量は、100~2000であることが好ましく、添加混合のしやすさ等の観点から、より好ましくは100~1000、さらに好ましくは300~1000である。
水性樹脂架橋剤含有液は、前記水性樹脂架橋剤、水性媒体、及び、必要に応じて添加される界面活性剤を含み、これら以外の任意成分として、本発明の効果を損なわない範囲において、水性樹脂架橋剤中の溶剤や添加剤とは別に、さらに、溶剤や、例えば、酸化防止剤、紫外線吸収剤、酸化防止剤、消泡剤等の添加剤が添加されてもよい。
水性樹脂架橋剤含有液は、前記水性樹脂架橋剤、水性媒体、及び、必要に応じて、界面活性剤、さらに、その他の成分の添加剤等を混合することにより、製造することができる。撹拌混合の方法は、特に限定されるものではなく、例えば、回転羽根やマグネチックスターラー等を用いた公知の方法により行うことができる。
混合時の温度や時間等の条件は、水性樹脂架橋剤の組成や水性媒体の種類等によって異なるが、効率的に均一に混合する観点から、例えば、水性樹脂架橋剤と水性媒体とを混合する場合には、20~100℃で0.5~5時間撹拌混合することが好ましい。
本発明の水性樹脂組成物は、前記水性樹脂架橋剤及び水性樹脂を含むものである。上述した本発明の水性樹脂架橋剤は、水性樹脂と併存させた状態での保存安定性に優れているため、前記水性樹脂組成物は、製造後長期間、少なくとも1週間程度経過した後でも、加熱等により架橋反応を良好に行うことができる。また、前記水性樹脂組成物を用いることにより、塗膜の硬度が高く、良好な耐溶剤性を有する水性樹脂の硬化物が得られる。
前記水性樹脂は、水溶性又は水分散性を有する樹脂である。前記水性樹脂は、水性樹脂架橋剤により架橋され得るものであり、特に、カルボジイミド基により架橋され得る架橋性基を有しているものであることが好ましい。
前記水性樹脂は、具体的には、架橋性基として、カルボキシ基、アミノ基及び水酸基から選ばれる官能基を有しているものであることが好ましく、アルコール性水酸基及び/又はカルボキシ基を有していることがより好ましい。前記水性樹脂としては、例えば、このような架橋性基を有する水性樹脂である、ポリエステル樹脂、アクリル樹脂、ポリウレタン樹脂、エポキシ樹脂、スチレン-アクリル樹脂、メラミン樹脂、ポリオレフィン樹脂、フッ素樹脂等が挙げられる。これらは、1種単独で用いても、2種以上を併用してもよい。これらのうち、ポリエステル樹脂、アクリル樹脂、ポリウレタン樹脂が、特に好適に用いられる。
水性樹脂組成物中の水性樹脂架橋剤の含有量は、水性樹脂の種類や、水性樹脂の硬化物に求められる物性等に応じて適宜定められるが、架橋反応性及びコストのバランス等の観点から、水性樹脂100質量部に対して、0.5~40質量部であることが好ましく、より好ましくは1~30質量部、さらに好ましくは1.5~20質量部である。
前記水性樹脂組成物は、前記水性樹脂架橋剤及び水性樹脂以外に、本発明の効果を損なわない範囲において、その他の成分を含んでいてもよい。具体的には、水性樹脂架橋剤又は水性樹脂架橋剤含有液中の溶剤や添加剤とは別に、使用目的や用途等に応じて、必要により、溶剤や、例えば、着色剤、充填剤、分散剤、可塑剤、増粘剤、紫外線吸収剤、酸化防止剤等の各種添加剤が、さらに添加されてもよい。
水性樹脂組成物は、前記水性樹脂架橋剤、水性樹脂、及び、前記のその他の成分等を、任意の順序で添加し、撹拌混合することにより、製造することができる。撹拌混合の方法は、特に限定されるものではなく、例えば、回転羽根やマグネチックスターラー等を用いた公知の方法により行うことができる。
混合時の温度や時間等の条件は、水性樹脂架橋剤の組成や水性樹脂の種類等によって異なるが、効率的に均一に混合する観点から、混合温度は0~100℃であることが好ましく、より好ましくは10~50℃である。水性樹脂架橋剤及び水性樹脂等の混合物の反応性や混合効率の観点から、20~30℃であることがより好ましい。混合時間は0.1~2時間であることが好ましく、より好ましくは0.3~1時間である。
なお、前記水性樹脂組成物は、水性樹脂との均一な混合性や取り扱い容易性等の観点から、上述したような水性樹脂架橋剤含有液として、水性樹脂と混合することにより製造してもよい。
前記水性樹脂組成物は、加熱等により架橋反応し、水性樹脂(水性樹脂組成物)の硬化物を生成する。前記硬化物は、水性樹脂組成物を所定の基材上に塗布した後、加熱して架橋反応させることにより、硬化膜として形成することができる。
水性樹脂組成物の塗布方法としては、公知の方法を用いることができ、例えば、刷毛塗り、タンポ塗り、吹付塗り、ホットスプレー塗り、エアレススプレー塗り、ローラ塗り、カーテンフロー塗り、流し塗り、浸し塗り、ナイフフェッジコート等を採用することができる。
加熱方法は、特に限定されるものではなく、例えば、電気加熱炉、赤外線加熱炉、高周波加熱炉等を用いることができる。加熱温度は、水性樹脂架橋剤の組成や水性樹脂の種類等に応じて、水性樹脂組成物が変色したり、熱分解したりしない範囲内において、架橋反応を促進する観点から適宜設定される。
例えば、前記水性樹脂組成物を塗料として適用することにより、高硬度の耐溶剤性に優れた水性樹脂の硬化膜(塗膜)が得られ、任意の基材上に、このような硬化膜が形成された物品を得ることもできる。なお、前記基材は、無機材料又は有機材料であるかを問わず、例えば、金属、セラミックス、樹脂、木材、布、繊維等の任意の材質でよい。
まず、下記実施例及び比較例で用いられる各ポリカルボジイミド化合物を合成した。
下記合成例において用いた原料化合物の詳細は、以下のとおりである。なお、本明細書における分子量は、計算値又はカタログ値である。
<ジイソシアネート化合物>
・HMDI:ジシクロヘキシルメタン-4,4’-ジイソシアネート(東京化成工業株式会社製、分子量262.35)
・TMXDI:テトラメチルキシリレンジイソシアネート(東京化成工業株式会社製、分子量244.29)
・IPDI:イソホロンジイソシアネート(東京化成工業株式会社製、分子量222.29)
・HDI:ヘキサメチレンジイソシアネート(東京化成工業株式会社製、分子量168.19)
・XDI:m-キシリレンジイソシアネート(東京化成工業株式会社製、分子量188.19)
・TDI:トリレンジイソシアネート(東京化成工業株式会社製、分子量174.16)
・MDI:4,4’-ジフェニルメタンジイソシアネート(東京化成工業(株)製、分子量250.25)
・MP550:ポリエチレングリコールモノメチルエーテル(東京化成工業株式会社製、分子量525~575)
・MP208:テトラエチレングリコールモノメチルエーテル(東京化成工業株式会社製、分子量208.25)
・CHI:シクロヘキシルイソシアネート(東京化成工業株式会社製、分子量125.17)
・C8:n-オクタノール(東京化成工業株式会社製、分子量130.23)
・BzOH:ベンジルアルコール(東京化成工業株式会社製、分子量108.14)
・IPA:イソプロパノール(東京化成工業株式会社製、分子量60.10)
・GM:グリコール酸メチル(東京化成工業株式会社製、分子量90.08)
・AA:N,N-ジエチルイソプロパノールアミン(東京化成工業株式会社製、分子量131.22)
・PEG400:ポリエチレングリコール400(東京化成工業株式会社製、分子量380~420)
・ED-900:ポリアルキレングリコールジアミン;「ジェファーミン(登録商標) ED-900」、ハンツマン・コーポレーション製、分子量900
・M-1000:ポリアルキレングリコールモノアミン;「ジェファーミン(登録商標) M-1000」、ハンツマン・コーポレーション製、分子量1000
・CHA:シクロヘキシルアミン(東京化成工業株式会社製、分子量99.18)
・3-メチル-1-フェニル-2-ホスホレン-1-オキシド(東京化成工業株式会社製)
<溶剤>
・シクロヘキサノン(東京化成工業株式会社製)
下記合成例における各分析は以下の装置及び方法にて行った。
<赤外吸収(IR)スペクトル>
・測定装置:「FTIR-8200PC」、株式会社島津製作所製
<重合度>
(1)ジイソシアネート化合物及び末端封止剤を同時に配合してポリカルボジイミド化合物を合成した場合は、カルボジイミド基の重合度は計算に基づく値である。
(2)ジイソシアネート化合物のポリカルボジイミド化反応によりイソシアネート末端ポリカルボジイミドを合成した後、末端封止剤を用いて末端イソシアネート基の封止反応を行い、ポリカルボジイミド化合物を合成した場合は、イソシアネート末端ポリカルボジイミドについて、電位差滴定法により(使用装置:自動滴定装置「COM-900」、平沼産業(株)製)、カルボジイミド基の重合度を求めた。具体的には、カルボジイミド化反応により得られたイソシアネート末端ポリカルボジイミドに、既知濃度のジ-n-ブチルアミンのトルエン溶液を混合して、末端イソシアネート基とジ-n-ブチルアミンとを反応させ、残存するジ-n-ブチルアミンを塩酸標準液で中和滴定し、イソシアネート基の残存量(末端NCO量[質量%])を算出した。この末端NCO量から、カルボジイミド基の重合度を求めた。
HMDI 100質量部、及びカルボジイミド化触媒0.5質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、170℃で18時間撹拌し、両末端にイソシアネート基を有するイソシアネート末端ポリカルボジイミド化合物(末端イソシアネート基量5.34質量%)を得た。IRスペクトル測定により波数2150cm-1前後のカルボジイミド基による吸収ピークを確認した。
得られたイソシアネート末端ポリカルボジイミド化合物85.6質量部を150℃で溶解し、これに、末端封止化合物としてMP550 59.9質量部(イソシアネート末端ポリカルボジイミド化合物の末端イソシアネート基と同モル当量)を添加し、180℃まで加熱して撹拌しながら2時間反応させた。反応生成物について、IRスペクトル測定により波数2200~2300cm-1のイソシアネート基による吸収ピークが消失したことを確認した後、反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(A1)を得た(Mn(数平均分子量理論値;以下、同様。):2672、1分子中のカルボジイミド基の数6)。
HMDI 100質量部、及びカルボジイミド化触媒0.5質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、170℃で6時間撹拌し、両末端にイソシアネート基を有するイソシアネート末端ポリカルボジイミド化合物(末端イソシアネート基量9.16質量%)を得た。IRスペクトル測定により波数2150cm-1前後のカルボジイミド基による吸収ピークを確認した。
得られたイソシアネート末端ポリカルボジイミド化合物87.4質量部を150℃で溶解し、これに、末端封止化合物としてMP550 104.8質量部(イソシアネート末端ポリカルボジイミド化合物の末端イソシアネート基と同モル当量)を添加し、180℃まで加熱して撹拌しながら2時間反応させた。反応生成物について、IRスペクトル測定により波数2200~2300cm-1のイソシアネート基による吸収ピークが消失したことを確認した後、反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(A2)を得た(Mn:2017、1分子中のカルボジイミド基の数3)。
HMDI 100質量部、及びカルボジイミド化触媒0.5質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、170℃で24時間撹拌し、両末端にイソシアネート基を有するイソシアネート末端ポリカルボジイミド化合物(末端イソシアネート基量3.77質量%)を得た。IRスペクトル測定により波数2150cm-1前後のカルボジイミド基による吸収ピークを確認した。
得られたイソシアネート末端ポリカルボジイミド化合物84.9質量部を150℃で溶解し、これに、末端封止化合物としてMP550 41.9質量部(イソシアネート末端ポリカルボジイミド化合物の末端イソシアネート基と同モル当量)を添加し、180℃まで加熱して撹拌しながら2時間反応させた。反応生成物について、IRスペクトル測定により波数2200~2300cm-1のイソシアネート基による吸収ピークが消失したことを確認した後、反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(A3)を得た(Mn:3328、1分子中のカルボジイミド基の数9)。
TMXDI 100質量部、及びカルボジイミド化触媒2.0質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、170℃で18時間撹拌混合して、カルボジイミド化反応を行い、両末端にイソシアネート基を有するイソシアネート末端ポリカルボジイミド化合物(末端イソシアネート基量5.81質量%)を得た。IRスペクトル測定により波数2150cm-1前後のカルボジイミド基による吸収ピークを確認した。
得られたイソシアネート末端ポリカルボジイミド化合物84.6質量部を150℃で溶解し、これに、末端封止剤としてMP550 64.3質量部(イソシアネート末端ポリカルボジイミド化合物の末端イソシアネート基と同モル当量)を添加し、180℃まで加熱して撹拌しながら2時間反応させた。反応生成物について、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基による吸収ピークが消失したことを確認した後、反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(A4)を得た(Mn:2564、1分子中のカルボジイミド基の数6)。
合成例1-1において、MP550を、MP208(11.3質量部)とMP550(30.0質量部)(合成例1-5)、AA(7.2質量部)とMP550(30.0質量部)(合成例1-6)、PEG400(43.6質量部)(合成例1-7)、ED-900(98.0質量部)(合成例1-8)、又はM-1000(108.9質量部)(合成例1-9)に変更し、それ以外は、合成例1-1と同様にして、ポリカルボジイミド化合物(A5)~(A9)をそれぞれ得た。
MDI 100質量部、及びMP550 62.8質量部、及び、溶媒としてシクロヘキサノン250質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、100℃で2時間撹拌混合して反応させた後、容器内温度25℃まで冷却した。カルボジイミド化触媒0.5質量部を投入し、再度加熱して、100℃で6時間撹拌混合して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基(NCO)の吸収ピークと波数2000~2200cm-1のカルボジイミド基(NCN)の吸収ピークの高さ比率([NCO]/[NCN]:ベースライン補正したピークの高さ比率;以下、同様。)が0.05以下に減少したことを確認した。
そして、溶媒を減圧留去して、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(A10)を得た(Mn:2588、1分子中のカルボジイミド基の数6)。
IPDI 100質量部、及びMP550 70.7質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、150℃で2時間撹拌混合して反応させた後、容器内温度25℃まで冷却した。カルボジイミド化触媒2.0質量部を投入し、再度加熱して、150℃で12時間撹拌混合して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基の吸収ピークと波数2000~2200cm-1のカルボジイミド基の吸収ピークの高さ比率が0.05以下に減少したことを確認した。
そして、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(A11)を得た(Mn:2392、1分子中のカルボジイミド基の数6)。
XDI 100質量部、及びMP550 83.5質量部、及び、溶媒としてシクロヘキサノン 300質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、150℃で2時間撹拌混合して反応させた後、容器内温度25℃まで冷却した。カルボジイミド化触媒2.0質量部を投入し、再度加熱して、150℃で12時間撹拌混合して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基の吸収ピークと波数2000~2200cm-1のカルボジイミド基の吸収ピークの高さ比率が0.05以下に減少したことを確認した。
そして、溶媒を減圧留去して、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(A12)を得た(Mn:2153、1分子中のカルボジイミド基の数6)。
TDI 100質量部、及びMP550 90.2質量部、及び、溶媒としてシクロヘキサノン280質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、100℃で2時間撹拌混合して反応させた後、容器内温度25℃まで冷却した。カルボジイミド化触媒0.5質量部を投入し、再度加熱して、100℃で12時間撹拌混合して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基の吸収ピークと波数2000~2200cm-1のカルボジイミド基の吸収ピークの高さ比率が0.05以下に減少したことを確認した。
そして、溶媒を減圧留去して、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(A13)を得た(Mn:2055、1分子中のカルボジイミド基の数6)。
IPDI 100質量部、CHI 28.2質量部、及びカルボジイミド化触媒2.6質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、150℃で24時間撹拌混合して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基の吸収ピークと波数2000~2200cm-1のカルボジイミド基の吸収ピークの高さ比率が0.05以下に減少したことを確認した。
そして、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(B1)を得た(Mn:920、1分子中のカルボジイミド基の数5)。
IPDI 100質量部、及びC8 19.5質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、150℃で2時間撹拌混合して反応させた後、容器内温度25℃まで冷却した。カルボジイミド化触媒2.0質量部を投入し、再度加熱して、150℃で24時間撹拌混合して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基の吸収ピークと波数2000~2200cm-1のカルボジイミド基の吸収ピークの高さ比率が0.05以下に減少したことを確認した。
そして、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(B2)を得た(Mn:1374、1分子中のカルボジイミド基の数5)。
合成例2-2において、C8を、BzOH(16.2質量部)(合成例2-3)、IPA(9.0質量部)(合成例2-4)、GM(6.8質量部)とMP208(15.6質量部)(合成例2-5)、又は、AA(9.8質量部)とCHA(7.4質量部)(合成例2-6)に変更し、それ以外は、合成例2-2と同様にして、ポリカルボジイミド化合物(B3)~(B6)をそれぞれ得た。
XDI 100質量部、CHI 33.3質量部、カルボジイミド化触媒2.7質量部、及び、溶媒としてシクロヘキサノン200質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、150℃で12時間撹拌混合して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基の吸収ピークと波数2000~2200cm-1のカルボジイミド基の吸収ピークの高さ比率が0.05以下に減少したことを確認した。
そして、溶媒を減圧留去して、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(B7)を得た(Mn:783、1分子中のカルボジイミド基の数5)。
TDI 100質量部、CHI 35.9質量部、カルボジイミド化触媒0.7質量部、及び、溶媒としてシクロヘキサノン200質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、150℃で12時間撹拌混合して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基の吸収ピークと波数2000~2200cm-1のカルボジイミド基の吸収ピークの高さ比率が0.05以下に減少したことを確認した。
そして、溶媒を減圧留去して、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(B8)を得た(Mn:727、1分子中のカルボジイミド基の数5)。
TMXDI 100質量部、及びカルボジイミド化触媒1.0質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、170℃で18時間撹拌混合して、カルボジイミド化反応を行い、両末端にイソシアネート基を有するイソシアネート末端ポリカルボジイミド化合物(末端イソシアネート基量6.74質量%)を得た。IRスペクトル測定により波数2150cm-1前後のカルボジイミド基による吸収ピークを確認した。
得られたイソシアネート末端ポリカルボジイミド化合物85.0質量部を150℃で溶解し、これに、末端封止剤としてC8 17.8質量部(イソシアネート末端ポリカルボジイミド化合物の末端イソシアネート基と同モル当量)を添加し、180℃まで加熱して撹拌しながら2時間反応させた。反応生成物について、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基による吸収ピークが消滅したことを確認した後、反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(B9)を得た(Mn:1506、1分子中のカルボジイミド基の数5)。
HMDI 100質量部、CHI 23.9質量部及びカルボジイミド化触媒0.6質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、180℃で47時間撹拌して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基の吸収ピークと波数2000~2200cm-1のカルボジイミド基の吸収ピークの高さ比率が0.05以下に減少したことを確認した。
そして、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(B’1)を得た(Mn:1080、1分子中のカルボジイミド基の数5)。
MDI 100質量部、CHI 25.0質量部、カルボジイミド化触媒0.6質量部、及び、溶媒としてシクロヘキサノン150質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、120℃で12時間撹拌混合して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基の吸収ピークと波数2000~2200cm-1のカルボジイミド基の吸収ピークの高さ比率が0.05以下に減少したことを確認した。
そして、溶媒を減圧留去して、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(B’2)を得た(Mn:1031、1分子中のカルボジイミド基の数5)。
HDI 100質量部、CHI 37.2質量部、及びカルボジイミド化触媒2.7質量部、及び、溶媒としてシクロヘキサノン200質量部を、還流管及び撹拌機付き反応容器に入れ、窒素気流下、150℃で12時間撹拌混合して反応させ、IRスペクトル測定にて、波数2200~2300cm-1のイソシアネート基の吸収ピークと波数2000~2200cm-1のカルボジイミド基の吸収ピークの高さ比率が0.05以下に減少したことを確認した。
そして、溶媒を減圧留去して、反応生成物を反応容器から取り出し、室温(25℃)まで冷却し、ポリカルボジイミド化合物(B’3)を得た(Mn:703、1分子中のカルボジイミド基の数5)。
上記合成例で得られた各ポリカルボジイミド化合物を用いて、水性樹脂架橋剤含有液を調製した。
下記実施例及び比較例で用いた界面活性剤の詳細は以下のとおりである。
<界面活性剤>
・C1:ドデシルベンゼンスルホン酸ナトリウム、アニオン性
・C2:N-ココイルメチルタウリンナトリウム、アニオン性
・C3:ラウリル硫酸ナトリウム、アニオン性
・C4:ポリオキシエチレン-2-エチルヘキシルエーテル、ノニオン性
ポリカルボジイミド化合物(A)、及びポリカルボジイミド化合物(B)を、下記表1に示す各種類及び配合量で、160℃で4時間撹拌混合した後、80℃に冷却し、イオン交換水150質量部で希釈して撹拌混合し、各水性樹脂架橋剤含有液を得た。
下記表1に示す各種類の、ポリカルボジイミド化合物(A)40質量部、及びポリカルボジイミド化合物(B)60質量部を160℃で4時間撹拌混合後、80℃に冷却し、界面活性剤の水溶液3質量部(有効成分換算)をそれぞれ添加して、イオン交換水150質量部で希釈して撹拌混合し、各水性樹脂架橋剤含有液を得た。
下記表1に示す各種類のポリカルボジイミド化合物(A)100質量部を60℃に加熱し、イオン交換水150質量部で希釈して撹拌混合し、各水性樹脂架橋剤含有液を得た。
上記実施例及び比較例で得られた各水性樹脂架橋剤含有液について、以下のようにして、シェルフライフ(保存安定性)の評価を行った。この評価結果を下記表2に示す。
〔シェルフライフ(保存安定性)〕
水性樹脂架橋剤含有液の製造直後及び40℃で90日間保管した後の粘度を測定した。製造直後の粘度に対する90日保管後の粘度の変化率を求めることにより、シェルフライフ(保存安定性)の評価を行った。
粘度の測定は、B型粘度計(「TVB-10M」、東機産業株式会社製;ローター:TM2、サンプル量50mL、温度20℃、回転数60rpm)にて行った。
粘度変化率を下記の評価基準で評価した。粘度変化率が0%に近いほど、保存安定性に優れており、評価AA~Cの場合は、保存安定性が良好であると言える。
評価結果を下記表1に示す。
<評価基準>
AA:粘度変化率5%未満
A:粘度変化率5%以上10%未満
B:粘度変化率10%以上20%未満
C:粘度変化率20%以上30%未満
D:粘度変化率30%以上50%未満
E:粘度変化率50%以上
(水性ポリウレタン樹脂組成物)
上記実施例及び比較例で製造した各水性樹脂用架橋剤含有液5質量部(架橋剤として2質量部)と、カルボキシ基含有水性ポリウレタン樹脂(「ハイドラン(登録商標) WLS-210」、DIC株式会社製、樹脂固形分35質量%)285質量部(樹脂固形分換算100質量部)とを撹拌混合し、水性ポリウレタン樹脂組成物をそれぞれ調製した。
上記実施例及び比較例で製造した各水性樹脂用架橋剤含有液5質量部(架橋剤として2質量部)と、カルボキシ基変性水性ポリエステル樹脂(「プラスコート(登録商標) Z-730」、互応化学工業株式会社製、樹脂固形分25質量%)400質量部(樹脂固形分換算100質量部)とを撹拌混合し、水性ポリエステル樹脂組成物をそれぞれ調製した。
上記実施例及び比較例で製造した各水性樹脂用架橋剤含有液5質量部(架橋剤として2質量部)と、カルボキシ基含有水性アクリル樹脂(「ボンコート(登録商標) VF-1060」、DIC株式会社製、樹脂固形分50質量%)200質量部(樹脂固形分換算100質量部)とを撹拌混合し、水性アクリル樹脂組成物をそれぞれ調製した。
上記において調製した各水性樹脂組成物について、以下に示す各種項目の評価を行った。これらの評価結果を下記表2に示す。
水性樹脂組成物の調製直後及び40℃で30日間保管した後の粘度を測定した。製造直後の粘度に対する30日保管後の粘度の変化率を求めることにより、ポットライフ(保存安定性)の評価を行った。
粘度の測定は、B型粘度計(「TVB-10M」、東機産業株式会社製;ローター:TM2、サンプル量50mL、温度20℃、回転数60rpm)にて行った。
粘度変化率を下記の評価基準で評価した。粘度変化率が0%に近いほど、保存安定性に優れており、評価A~Cの場合は、保存安定性が良好であると言える。
<評価基準>
AA:粘度変化率10%未満
A:粘度変化率10%以上20%未満
B:粘度変化率20%以上30%未満
C:粘度変化率30%以上50%未満
D:粘度変化率50%以上100%未満
E:粘度変化率100%以上
水性樹脂組成物を、離型ポリエチレンテレフタレート(PET)フィルム上に、バーコーター(ワイヤーロッドNo.32)を用いて塗布し、80℃で10分間乾燥させた後、室温(25℃)で1日間放置して、塗膜を形成した。
前記塗膜を、前記離型PETフィルムから剥離したものを塗膜試験片とした。
前記塗膜試験片について、下記に示す引張試験及び鉛筆硬度試験を行い、これらの試験結果を総合して、塗膜硬度を評価した。
(1)引張試験
引張試験機(卓上形精密万能試験機「AGS-X」、株式会社島津製作所製;引張速度100mm/min;試験片サイズ:ダンベル状 JIS 4号形、厚さ30μm;チャック間50mm)で引張試験を行い、塗膜試験片10点について、引張弾性率を測定した。
水性樹脂架橋剤非添加の塗膜(ブランク)についても、同様にして引張弾性率を測定し、ブランクの引張弾性率に対する塗膜試験片の引張弾性率の比率(倍数)を求め、下記の点数基準により点数化して評価し、塗膜試験片10点についての平均点を求め、これを評価点とした。
<点数基準>
4点:引張弾性率2.0倍超
3点:引張弾性率1.5倍超2.0倍以下
2点:引張弾性率1.2倍超1.5倍以下
1点:引張弾性率1.0倍超1.2倍以下
0点:引張弾性率1.0倍未満
JIS K 5600-5-4:1999に準じて、鉛筆硬度試験機を用いて、塗膜試験片10点について、鉛筆硬度を測定した。
測定した鉛筆硬度を下記の点数基準により点数化し、塗膜試験片10点についての平均点を求め、これを評価点とした。
<点数基準>
4点:鉛筆硬度2H~
3点:鉛筆硬度F~H
2点:鉛筆硬度HB~3B
1点:鉛筆硬度4B~5B
0点:鉛筆硬度6B
<評価基準>
A:4点
B:3点以上4点未満
C:2点以上3点未満
D:1点以上2点未満
E:1点未満
水性樹脂組成物を、アルミニウム板上に、バーコーター(ワイヤーロッドNo.32)を用いて塗布し、80℃で10分間乾燥させたものを塗膜試験片とした。
前記塗膜試験片について、摩擦試験機(「FR-1B」、スガ試験機株式会社製)にて、70質量%エタノール水溶液を染み込ませた脱脂綿(荷重900g/cm2)を往復50回ダブルラビングする摩擦試験を行った。
摩擦試験後の塗膜試験片を目視観察し、白化性及び塗膜残存面積割合の各評価項目について、下記の点数基準にて点数化し、塗膜試験片2点についての平均点を求め、これを評価点とした。これらの評価項目を総合して、塗膜の耐溶剤性を評価した。
<点数基準>
(1)白化性
5点:変化なし
4点:薄いラビング痕あり、又はわずかな白化
3点:一部白化
2点:全体白化
1点:一部溶解
0点:完全溶解
(2)塗膜残存面積割合
5点 :100%
4.5点:95%以上100%未満
4点 :85%以上95%未満
3.5点:75%以上85%未満
3点 :60%以上75%未満
2.5点:45%以上60%未満
2点 :40%以上45%未満
1.5点:25%以上40%未満
1点 :10%以上25%未満
0点 :10%未満
<評価基準>
A:5点
B:4点以上5点未満
C:3点以上4点未満
D:2点以上3点未満
E:2点未満
上記実施例及び比較例で調製した水性樹脂組成物を、アルミニウム板上に、エアースプレーにて塗布し(乾燥膜厚30μm)、10分間のセッティングを行った。その上に、同じ水性樹脂組成物を、エアースプレーにて塗布し(乾燥膜厚15μm、合計45μm)、80℃で3分間のプレヒートを行い、下塗りした。下塗りの塗工膜(未硬化塗膜)の上に、2液硬化型ポリウレタンクリア塗料(「ボデーペンウレタンクリア」、株式会社ソフト99コーポレーション製)を上塗りし(乾燥膜厚30μm)、80℃で焼き付けて、複層塗膜(ウェット・オン・ウェット塗装による硬化膜)を形成した。
前記複層塗膜は、いずれの水性樹脂組成物を用いた場合も、目視観察による異常は認められなかった。
上記においてウェット・オン・ウェット塗装で作製した複層塗膜について、下記に示す方法により層間付着性の評価を行った。この評価結果も下記表2に併せて示す。
前記複層塗膜の下塗り塗膜の層と上塗り塗膜の層との層間の付着性を、ASTM D3359-17に準じたクロスカット試験(碁盤目試験)により評価した。
試験条件は、前記複層塗膜に、2mm間隔で6×6の碁盤目をカッターで作成し、25℃にて、粘着力6.7N/cmのテープを貼り付け、テープを剥がした時の剥離状態(剥離面積割合)に基づいて、下記の評価基準で層間付着性の評価を行った。剥離面積割合が小さいほど、層間付着性が高く、評価A~Cの場合は、層間付着性が十分に高いと言える。
<評価基準>
A:剥離面積割合0%
B:剥離面積割合0%以上5%未満
C:剥離面積割合5%以上15%未満
D:剥離面積割合15%以上35%未満
E:剥離面積割合35%以上
Claims (18)
- ポリカルボジイミド化合物(A)及びポリカルボジイミド化合物(B)を含有し、
前記ポリカルボジイミド化合物(A)は、両末端のイソシアネート基がそれぞれ親水性有機化合物で封止された構造であり、前記親水性有機化合物の少なくとも一方が分子量340以上であり、
前記ポリカルボジイミド化合物(B)は、シクロヘキシル環1個又はベンゼン環1個を有するジイソシアネート化合物を構造単位とし、両末端のイソシアネート基がそれぞれ分子量300以下の有機化合物で封止された構造であり、
前記ポリカルボジイミド化合物(A)及び前記ポリカルボジイミド化合物(B)の合計100質量部中の前記ポリカルボジイミド化合物(A)が5~90質量部である、水性樹脂架橋剤。 - 分子量340以上の前記親水性有機化合物が、下記式(1)で表される化合物である、請求項1に記載の水性樹脂架橋剤。
R1(OCHR2CH2)nOH (1)
(式(1)中、R1は、炭素数1~20の、アルキル基、シクロアルキル基又はアリール基である。R2は、水素原子又はメチル基である。nは7~30の数である。) - 前記式(1)中、R1がメチル基であり、R2が水素原子である、請求項2に記載の水性樹脂架橋剤。
- 分子量300以下の前記有機化合物が、イソシアネート基と反応する官能基を1個有する化合物である、請求項1~3のいずれかに記載のカルボジイミド系水性樹脂架橋剤。
- 分子量300以下の前記有機化合物が、第一級又は第二級のモノアミン、モノイソシアネート、モノオール、モノエポキシド及びモノカルボン酸から選ばれる化合物である、請求項1~4のいずれか1項に記載の水性樹脂架橋剤。
- 前記ジイソシアネート化合物が、第一級イソシアネート基を有する化合物である、請求項1~5のいずれか1項に記載の水性樹脂架橋剤。
- 請求項1~6のいずれか1項に記載の水性樹脂架橋剤、及び水性媒体を含む、水性樹脂架橋剤含有液。
- 前記水性媒体が、水、又は水と親水性溶媒との混合溶媒である、請求項7に記載の水性樹脂架橋剤含有液。
- さらに界面活性剤を含有する、請求項7又は8に記載の水性樹脂架橋剤含有液。
- 前記界面活性剤が、アニオン性界面活性剤である、請求項9に記載の水性樹脂用架橋剤含有液。
- 前記アニオン性界面活性剤が、アルキルベンゼンスルホン酸塩、アルキル硫酸塩、及びN-ココイルメチルタウリンナトリウムから選ばれる1種以上である、請求項10に記載の水性樹脂用架橋剤含有液。
- 請求項1~6のいずれか1項に記載の水性樹脂架橋剤、及び水性樹脂を含む、水性樹脂組成物。
- 前記水性樹脂が、カルボキシ基、アミノ基及び水酸基から選ばれる官能基を有する、請求項12に記載の水性樹脂組成物。
- 前記水性樹脂が、ポリエステル樹脂、アクリル樹脂、ポリウレタン樹脂、エポキシ樹脂、スチレン-アクリル樹脂、メラミン樹脂、ポリオレフィン樹脂及びフッ素樹脂から選ばれる1種以上である、請求項12又は13に記載の水性樹脂組成物。
- 接着剤、繊維処理剤、コーティング剤、インキ、塗料又は粘着剤に用いられる、請求項12~14のいずれか1項に記載の水性樹脂組成物。
- ウェット・オン・ウェット方式の塗装用である、請求項12~14のいずれか1項に記載の水性樹脂組成物。
- 請求項12~16のいずれか1項に記載の水性樹脂組成物により形成された硬化膜。
- 請求項17に記載の硬化膜が、基材上に形成されてなる物品。
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US2941956A (en) | 1956-08-15 | 1960-06-21 | Socony Mobil Oil Co Inc | Regeneration of contact material |
JPS4733279B1 (ja) | 1968-12-20 | 1972-08-24 | ||
WO2017006950A1 (ja) * | 2015-07-08 | 2017-01-12 | 日清紡ケミカル株式会社 | カルボジイミド系水性樹脂架橋剤 |
WO2017217542A1 (ja) * | 2016-06-16 | 2017-12-21 | ミドリ安全株式会社 | 手袋の製造方法、手袋、及び手袋用エマルション組成物 |
WO2020179835A1 (ja) * | 2019-03-05 | 2020-09-10 | 日清紡ケミカル株式会社 | 水性樹脂架橋剤、水性樹脂架橋剤含有液及び水性樹脂組成物 |
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Patent Citations (5)
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US2941956A (en) | 1956-08-15 | 1960-06-21 | Socony Mobil Oil Co Inc | Regeneration of contact material |
JPS4733279B1 (ja) | 1968-12-20 | 1972-08-24 | ||
WO2017006950A1 (ja) * | 2015-07-08 | 2017-01-12 | 日清紡ケミカル株式会社 | カルボジイミド系水性樹脂架橋剤 |
WO2017217542A1 (ja) * | 2016-06-16 | 2017-12-21 | ミドリ安全株式会社 | 手袋の製造方法、手袋、及び手袋用エマルション組成物 |
WO2020179835A1 (ja) * | 2019-03-05 | 2020-09-10 | 日清紡ケミカル株式会社 | 水性樹脂架橋剤、水性樹脂架橋剤含有液及び水性樹脂組成物 |
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Title |
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CHEMICAL REVIEW, vol. 81, no. 4, 1981, pages 619 - 621 |
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