TW200932776A - Aqueous polyurethane resin, coating film, and artificial and synthetic leather - Google Patents

Abstract

Disclosed is an aqueous polyurethane resin which is obtained by a reaction between a prepolymer having a terminal isocyanate group and a chain extender. The prepolymer having a terminal isocyanate group is obtained by reacting at least a polyisocyanate, which contains not less than 50% by mole of isocyanate groups of 1,4-bis(isocyanatomethyl)cyclohexane relative to the total mole number of the isocyanate groups, a high-molecular-weight polyol, and an active hydrogen compound containing a hydrophilic group.

Description

200932776 VI. Description of the Invention: [Technical Field of the Invention] From the aqueous polyamine polyurethane resin, the present invention relates to an aqueous polyurethane resin and a formic acid vinegar resin. Artificial and synthetic leather made from water-based fat. [Prior Art] From the viewpoints of environmental protection, environmental protection, safety, etc., the water-based tree water-based polyaminocarboxylic acid brewing tree is popular in coatings from the viewpoints of excellent durability and resistance to abrasion and abrasion resistance. , in the field of adhesives, adhesives or coating agents. However, the right aqueous polyamine group? When the acid ester application is applied at a high speed, the shearing force occurring in the treatment cannot be withstood, and the occurrence of agglomerates may occur; the brother/month can be stably dispersed even under high shear force. Further, it is possible to suppress an aqueous polyurethane sulfonate resin which is excellent in dispersion stability of condensate generation. Furthermore, the coating film obtained from the aqueous polyurethane carboxylic acid resin is lower in water resistance, lower in water resistance, and heat resistance than the coating film obtained from the solvent-type polyurethane vinegar resin. Durability is also insufficient, and we look forward to further improvements. Related to the above requirements, you 丨] If the case has the following (AMC) water-based polyamines =: ΓΑ) contains (1) polyiso-acid vinegar, (5) high molecular weight active and (mountain) hydrophilic oxidized Peggy The pre-097143467 200932776 polymer of the alcohol or the polyamine '(B) is water' (C) optionally contains a reaction product of a chain extender and/or a surfactant; wherein the amount of the reaction product in the dispersion is 40~ 6〇% by mass (for example, refer to Patent Document 1 below); a preferred polyisocyanate is, for example, 1,3-bis(isocyanate), which is a double (iso)曰 曰 甲基 甲基 甲基 、 、 乳酸 乳酸 乳酸 乳酸 乳酸 乳酸 乳酸 乳酸 乳酸 乳酸 乳酸 乳酸 乳酸 ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ The aqueous polyurethane resin described above is still insufficient in dispersion stability and heat resistance, and it is expected that the above-mentioned water-based polyurethane resin can be further improved. Further, the coating film obtained from the aqueous polyurethane resin is provided. A problem of viscous (sticky and slippery) is produced. The object of the present invention is An aqueous polyurethane resin which is excellent in dispersion stability, solvent resistance and heat resistance, and which can realize an excellent hand, and (4) obtained from the hydrophobic polyamine ruthenium sulphate and the use thereof Artificial and synthetic leather of polyamino phthalate resin. (Means for solving the problem) For the above purpose of the nucleus, the aqueous polyurethane urethane resin of the present invention is an isocyanate-terminated prepolymer (which is at least The ratio of the total mo-hetero 1 50 mol% or more relative to the oleic acid vinegar group is bis (iso-acid methyl). The sulphuric acid isocyanate-based polyisocyanate is high. The molecular weight poly & alcohol and the hydrophilic group-containing active cerium compound are obtained by reacting with a bond extender in 097143467 4 200932776. Further, among the aqueous polyamino phthalate resins of the present invention, the most 5质量%。 The mass of the above-mentioned chain of the present invention is more preferably 0. 05~1. 5质量% Further, in the aqueous polyurethane of the present invention, the resin Preferably, the chain extender is a compound represented by the following general formula (1): ❹ General formula (1): [Formula 1] (wherein R1 and R2 are the same or mutually different carbon number 4 alkane And R4 are the same or different carbon number of the alkyl group. m is the integer β of the formula 3) Further, in the aqueous polyamine phthalate resin of the present invention, it is preferably 丨, 4 A pair of hydrazine (isocyanatoguanidino) cyclohexane is contained in the form of trans], 4_bis(isocyanatomethyl)cyclohexane of 50% by mass or more. Further, the coating film system of the present invention Further, the above-described aqueous polyurethane resin is used in the artificial and synthetic leather of the present invention. * (Effect of the invention) The aqueous polyamine phthalic acid according to the present invention Ester resin can improve dispersion, stability, solvent resistance and heat resistance, and achieve excellent hand feeling. Therefore, the coated film, artificial and synthetic leather of the present invention which utilizes these characteristics can be provided. [Embodiment] The aqueous polyaminophthalic acid ester resin of the present invention is obtained by a reaction of an isocyanate-based terminal prepolymer and a chain extender. The isononanoate-based terminal prepolymer is obtained by reacting at least a polyisocyanate, a high molecular weight polyol, and a hydrophilic group-containing active hydrogen compound. In the present invention, the polyisocyanate is based on the total number of moles of isocyanate groups, and the isocyanate group of 1'4-bis(isocyanatononyl)cyclohexane is 5 〇 mol% or more (preferably 70 mol%). The above is particularly preferably contained in a ratio of 8 〇 mol% or more, and more preferably Mole %. It is especially good to contain 1% of Mo. 1' 4-bis(isocyanatoguanidino)cyclohexane is cis-^-bisguanidinoisocyanyl)cyclohexane (hereinafter referred to as "cis-indole, 4-body") and trans - a stereoisomer of 14 bis(isocyanatoinyl)cyclohexane (hereinafter referred to as "trans oxime, 4 body"), 10 1,4-bis(isocyanatoguanyl) in the present invention The cyclohexane system preferably contains 50% by mass or more of the trans 1,4 body, particularly preferably 7 % by mass, more preferably 8 % by mass or more. It is especially preferable to contain 90% by mass. The 1,4-bis(isocyanatomethyl)cyclohexane system can be used, for example, as described in Japanese Patent Laid-Open No. Hei 7-3_27, the cold-hot two-stage method (form method) or the salt-making method, or the Japanese patent. A method of using phosgene or the like described in Japanese Laid-Open Patent Publication No. 2004-244349 or the like is disclosed. 097143467 6 200932776 Further, among the above polyisocyanates, polyisocyanates which can be used in combination with 1,4-bis(isocyanatononyl)cyclohexane include, for example, 1,3-diisocyanate cyclopentane. Ester, cyclohexyl 1,4-diisocyanate, cyclohexyl 1,3-diisocyanate, 3-isocyanatodecyl-3,5,5-trimethylcyclohexyl isocyanate, 4, 4'-arylene di(cyclohexyl isocyanate), decyl-2,4-diisocyanate cyclohexyl ester, methyl-2,6-diisocyanate cyclohexyl ester, 1,3-double (iso) Cyanate methyl)cyclohexane, 1,3-bis(isocyanatoethyl)cyclohexane, 1,4-bis(isocyanatoethyl)cyclohexane, 2, 5-indole or An alicyclic diisocyanate such as 2,6-bis(isocyanatodecyl) norbornane, and mixtures thereof. Further, for example, triammonium diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-diisocyanate, 1,2-di Butyl isocyanate, butyl 2, 3-diisocyanate, 1,3-diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate An aliphatic diisocyanate such as 2,6-diisocyanate methylhexanoate. Further, in the range of not impairing the film formability of the aqueous polyurethane resin, the polyisocyanate, the ureido phthalate, the biuret, the quinone trione can also be used in combination. And diisocyanate di complex modified body. Further, a monoisocyanate may be used in combination insofar as it does not impair the dispersion stability, solvent resistance, heat resistance and hand feeling of the aqueous polyurethane resin. Examples of the monoisocyanate include decyl isocyanate, ethyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, and benzene isocyanate. Ester, 'benzyl isocyanate, etc. Polyisocyanate capable of being used in combination with 1,4-bis(isocyanatomethyl)cyclohexane, 097143467 7 200932776 Preferably, for example, isocyanato-3-isocyanatoguanidino-3, 5, 5- Trimethylcyclohexyl ester (alias: isophorone diisocyanate (IPDI)), 4, 4'-fluorenylene bis(cyclohexyl isocyanate), 1,4-cycloisocyanate cyclohexyl ester, 1, 3 - bis(isocyanatodecyl)cyclohexane, 2,5 or 2,6-bis(isocyanatomethyl)norbornane and mixtures thereof, hexamethylene diisocyanate, and the like A modified body of polyisocyanate. Further, 1,3-bis(isocyanatononyl)cyclohexane is cis-1,3-bis(isocyanatomethyl)cyclohexane (hereinafter referred to as "cis 1,3 body". And a stereoisomer of trans-1,3-bis(isocyanatoinyl)cyclohexane (hereinafter referred to as "trans 1,3"), when 1,3-bis(isocyano) In the case where the acid thiol) cyclohexane is used in combination with 1,4-bis(isocyanatomethyl)cyclohexane, the 1,3-bis(isocyanatomethyl)cyclohexane system preferably contains a counter. The formula 1 and the 3 body are 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more. In the present invention, the high molecular weight polyol is a compound having two or more hydroxyl groups and having a uniform molecular weight of 400 or more, such as a polyether polyol, a polyester polyol, or a polycarbonate polyol. The number average molecular weight of the high molecular weight polyol is, for example, 400 to 5,000, preferably 1400 to 3,000, particularly preferably 1,500 to 2,500, and the hydroxyl group is, for example, HM 25 mgKOH/g. The polyether polyol may, for example, be polypropylene glycol or polytetradecyl ether glycol. * Polypropylene glycol is preferably a polyoxyalkylene polyol having a nitrous oxide compound as a catalyst as described in Japanese Patent No. 3905638, and having a lower by-product yield of 097143467 8 200932776. The polypropylene glycol is, for example, a low molecular weight polyol or a low molecular weight polyamine as a starting agent, and mainly an epoxy resin addition polymer, if necessary, together with epoxy bake (ie, including epoxy species and epoxy B (IV) Random and / / paragraph segmentation ❹

Further, the low molecular weight polyol is a compound having two or more and a number average molecular weight of 60 to less than 400, and examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, and 1,3-butanediol. , butanediol, i 6-hexanediol, neopentyl glycol, 3-methyl-1'5-pentanediol, burnt (7-22) glycol, diethylene glycol, triethylene glycol, two Propylene glycol, or U-cyclohexanediketanol and mixtures thereof; U 4-cyclohexanediol, 2-diol coffee, hydrogenated dip-a, 1,4-dihydroxy-2-butene, 2 a diol such as 6-dimethyl + octene _3,8-diol or bisphenol A; or a trihydric alcohol such as glycerol or trimethyl propyl hydride; or, for example, tetramethyl methacrylate The read, diquaternal fine alcohol, D-sandol, xylitol, D-glycol, D-mannose have 4 to read a (tetra)ol and the like. Further, examples of the low molecular weight polyamine include a lipid (tetra)diamine such as ethylenediamine; or an aromatic diamine such as toluenediamine or the like. The polytetramethyl ether glycol may, for example, be a ring-opening polymer obtained by concentrating a tetrahydrobone surface cationic agent, or an amorphous polytetramethylene copolymerizing a polymerization unit of a shunting substance with the above-mentioned diol. Ethylene ether glycol and the like. The polycondensate is a polycondensate obtained by reacting the above polyol with a polybasic acid under known conditions. 097143467 9 200932776 The polybasic acid may, for example, be oxalic acid, malonic acid, succinic acid, mercapto succinic acid, glutaric acid, adipic acid, 1,1-dimercapto-1,3-dicarboxypropane, 3- Mercapto-3-ethylglutaric acid, sebacic acid, sebacic acid, other aliphatic dicarboxylic acids (carbon number 11 to 13), suberic acid, eleven adipic acid, dodecanedioic acid, 13th hospital diacid, tetradecanoic acid, pentadecanedioic acid, octadecanedioic acid, nonadelonal acid, eicosanedioic acid, decyl adipate, citraconic acid, bismuth dimerization Acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, terpene dicarboxylic acid, dimer acid, high acid, A carboxylic acid such as pimelic acid, an acid anhydride derived from the carboxylic acid, an acid halide, ricinoleic acid, 12-hydroxystearic acid or the like. In addition, the polyester polyol may be, for example, a polycondensation obtained by ring-opening polymerization of an internal vinegar such as ε-hexene or 7-valerolactone using the above-mentioned diol as a starting agent. An ester polyol, a polyvalerolactone polyol, and a lactone-based polyol which copolymerizes these with the above-mentioned diol.聚碳酸酯 The polycarbonate polyol may, for example, be a ring-opening polymer of ethylene carbonate using the above-mentioned diol as a starting agent; or, for example, 1,3-propanediol, 1,4-butanediol, 1,5 An amorphous polycarbonate polyol in which a glycol such as pentanediol or 1,6-hexanediol is copolymerized with a ring-opening polymer. These high molecular weight polyols may be used alone or in combination of two or more. In addition, among these, a polycarbonate polyol is preferable, and a polycarbonate diol is preferable, and an amorphous (normal temperature liquid) polycarbonate diol is more preferable. In the present invention, the active hydrazine compound containing a hydrophilic group is a compound containing a hydrophilic group 097143467 10 200932776 and an active argon group, and the hydrophilic group may, for example, be an anionic group, a cationic group or a nonionic group. The active hydrogen group is a group which reacts with an isocyanate group, and examples thereof include a hydroxyl group, an amine group, a carboxyl group, and an epoxy group. The active hydrogen compound containing a hydrophilic group may, for example, be an active hydrogen compound containing a carboxylic acid group, an active hydrogen compound containing a sulfonic acid group, an active hydrogen compound containing a hydroxyl group, a polybasic acid containing a hydrophilic group, or the like. Polyoxyethylene-based active hydrogen compound.

Examples of the active hydrogen compound containing a carboxylic acid group include 2,2-dihydroxymethylacetic acid, 2,2-dihydroxydecyllactic acid, and 2,2-dihydroxydecylpropionic acid (hereinafter referred to as "DMPA"). a dihydroxycarboxylic acid such as 2,2-dihydroxyindolebutyric acid (hereinafter referred to as "MBA"), 2,2-dihydroxymethylbutyric acid or 2,2-dihydroxymethylpentanoic acid; or, for example, an amine a diaminocarboxylic acid such as an acid or a arginine; or a metal salt or a salt thereof. Preferably, it is 2,2--light methylpropionic acid (DMPA), 2,2-di-methylbutyric acid (DMBA). The active hydrogen compound containing a sulfonic acid group is obtained, for example, by a synthetic reaction of an epoxy group-containing compound with an acidic sulfite such as dimercaptobutyl acid or dihydroxypropanesulfonic acid. Further, for example, Yibubis(2-hydroxyethyl)-L-aminoethanesulfonic acid, N,N-bis(2-hydroxyethyl)_2-aminobutanesulfonate^^ 3-phenylenediamine -4,6-disulfonic acid, diaminobutanesulfonic acid, diaminopropanesulfonic acid, 3|6-diamino-2-indenenesulfonic acid, 2,4-diamino-5-toluene Acid, 1^_(2__aminoethyl)-2-aminoethyl acid, 2-aminoethyl acid, di(2-aminoethyl)-2-aminobutanesulfonic acid, or the like Metal salts of sulfonic acids, ammonium salts, and the like. 097143467 200932776 The active hydrogen compound containing a hydroxyl group is, for example, N-(2-aminoethyl)ethanolamine. The polybasic acid containing a hydrophilic group is, for example, a polybasic acid containing a sulfonic acid, and more specifically, for example, 5-monosulfonic acid, sulfophthalic acid, 4-sulfophthalic acid Formic acid, 5-(p-sulfophenoxy)isophthalic acid, 5-(sulfopropoxy)isophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfopropyl malonic acid Sulfosuccinic acid, 2-sulfobenzoic acid, 2,3-sulfobenzoic acid, 5-sulfohydrazine salicylic acid, and alkyl esters of such carboxylic acids, and metal salts of such sulfonic acids , money and salt, etc. It is preferably a sodium salt of 5-de-isophthalic acid or a sodium salt of 5-diphenyl phthalate. The active hydrogen compound containing a polyoxyethylene group contains a polyoxyethylene group and a compound having two or more active hydrogen groups in a main chain or a side chain. The polyoxyethylene group-containing compound is, for example, polyethylene glycol (e.g., a number average molecular weight of 2 GG to 〇 ’ 最好), and a polyhydric alcohol containing a polyoxyethylene side chain. The polyol-containing side chain containing a polyoxyethylene side chain containing a polyoxyethylene group and having two or more active hydrogen groups can be synthesized as follows. That is, the above-mentioned monoisocyanate is first blocked with a single-sided terminal blocking polyoxyethylene glycol (for example, alkoxyethylene glycol sealed by a single-side end using an alkyl group having 1 to 4 carbon atoms, and the number average molecular weight is 2 〇〇 to 6 〇). 〇〇, preferably 3〇〇~3〇〇〇”, ethyl hydroxyformate is blocked with respect to the hydroxyl group of the polyoxyethylene glycol at one end, and the excess of the isocyanate group of diisocyanate The reaction, if necessary, removes the polyisocyanate containing polyoxyethylene chain by removing the diisocyanate which is not reacted with 097143467 12 200932776. Next, the polyisocyanate-containing monoisocyanate and the dialcoholamine (for example) Diethanolamine, etc.] is based on the secondary amine group of the dialcoholamine, and is subjected to a urea conversion reaction in a ratio equivalent to the isocyanate group of the polyoxyethylene group. The polyisocyanate of the polyoxyethylene side chain polyol is preferably, for example, an aliphatic diisocyanate m or a 丨'4-bis(isocyanate fluorenyl group) such as methylene diisocyanate. Cyclohexane (HeXDI) or a mixture of these isocyanate 3-isocyanide Acid ester fluorenyl _3,55_trimethylcyclohexyl ester (alias diisophor _diiso l« (IPDI)), 4,4, _arylene bis (cyclohexyl Us day) (H12MDI) , 2, 5- or 2, 6-bis (isocyanate-based mercapto), rice-fired (_) or the mixture of alicyclic di-isomers, etc., especially HD I is preferred. In the case of compounding a compound containing a polyoxyethylene group, the content of the polyoxyethyl group relative to the aqueous polyaminomethyl (tetra) tree is, for example, 0% by mass, preferably (4)% by mass, especially 2 to 10% by mass is preferred. The active hydrogen compound having a hydrophilic group of 3 or the like may be used singly or in combination. Further, among these, it is preferably an active nitrogen compound containing a (tetra) group and an active hydrogen compound containing a polyoxyethylene group. And j can obtain an isocyanate-based terminal prepolymer, for example, a polyisocyanate group polyol and a Wei water-containing hydrogen-requiring compound, % σ 'solu A known polymerization method such as polymerization is carried out to carry out the reaction 097143467 13 200932776 = 卜 Right: the active hydrogen compound having a hydrophilic group is contained in the high molecular weight polybasic compound], and the isocyanate is obtained by reacting the stilbene 1 and 7 alcohol with polyisocyanic acid. Base end prepolymer. For example, in the synthesis of the polyester polyol y, an active hydrogen compound having 3 hydrophilic groups in the high molecular weight polyol can be obtained by the polyol which is blended with the hydrophilic group-containing active oxygen compound. Furthermore, for example, the above polyester multi-boiler

In the synthesis of a non-alcoholic alcohol, an active hydrogen compound having a hydrophilic group of 3 in a high molecular weight polyol can also be obtained by a polybasic acid containing a hydrophilic group. Further, for example, in the synthesis of a polyester polyol, a polyether polydone, a polycarbonate polyol, a zebra oxime, and a oxime alcohol obtained by using a ring-opening ring, the compound is blended. The starting agent or the copolymerized component is transmitted, and the active hydrogen compound containing a hydrophilic group is also used, and the active hydrogen compound containing a hydrophilic group in the high molecular weight and multi-invasion is also caused by the active argon compound having 3 hydrophilic groups. For example, a polyether polyol (preferably polytetradecyl ether glycol) can be used to react with a molecular weight polyol, and the high molecular weight polyol can also contain an active hydrogen compound having a hydrophilic group. The above-mentioned respective components are active hydrogen groups (hydroxyl groups, amine groups, and the like) with respect to the high molecular weight polyol and the active hydrogen compound containing a hydrophilic group (in the case of blending a low molecular weight polyol described later, the low molecular weight polyol is included) The hydroxy), polyisocyanate isocyanate group equivalent ratio (isocyanate group / active hydrogen group) is, for example, 1. 1~2· 5 (preferably 1. 2~2. 3, especially preferably 1·2~2) Proportion into 097143467 14 200932776 line deployment (current). If the equivalent ratio of the isocyanate group is within this range, the dispersion stability of the aqueous polymer resin can be improved. Thus, is the aqueous polyamine group used? _ _ _, you can get hand _, artificial leather and synthetic leather. In the overall polymerization, for example, under a nitrogen stream, a high molecular weight polyol and a hydrophilic group-containing active hydrogen compound are added thereto while stirring the polyisocyanate, and the reaction temperature is 5 (M3 (TC ( It is best to do not. C) carry out the reaction for about 3 to 15 hours. When the 'gluten solution polymerization' is added to the organic solvent, the polyisocyanate, the polymer polyol and the hydrophilic group-containing active hydrogen compound are added according to the reaction temperature 5 ( M20 ° C (preferably 5 〇 ~ 8 〇. 〇 carry out the reaction for about 3 to 15 hours. The organic solvent is inactive to the isocyanate group, rich in hydrophilicity and easy to remove low / fluorene solvent, for example: acetone Or methyl ethyl ketone, etc.; or, for example, tetrahydroguanidine squamous methyl sulphate _, ethyl sulphonic acid sucrose, etc.; or, for example, decyl carbitol acetate, ethyl carbitol acetate vinegar Such as carbitol acetate lysine; or nitrile such as acetonitrile; esters such as ethyl acetate, butyl acetate, etc. 曰 者 ' 'In the above polymerization reaction, the purpose and use, can also be appropriately formulated into the above low molecular weight polyol Furthermore, the above polymerization reaction In addition, a known amine phthalate catalyst such as an amine system, a tin system, a lead system or a lanthanide group may be added as needed, and is liberated from the obtained amic acid hydroxy end group prepolymer (not Reaction) Polyisocyanate 'II: 097143467 15 200932776 For example, a known removal means such as distillation or extraction is carried out. Further, 'in the end of the heterogeneous county-end parental towel, when the hydrophilic group contains an anionic group or a rider group In the case of a neutralizing agent, it is preferable to add a neutralizing agent to form an anionic group or a cationic group. W. When an anionic group is contained, the neutralizing agent is, for example, a conventional test, for example, an organic test [for example, three Amines (trimethylamine, triethylamine, etc., such as tri-C1-4 alkylamine, dimethylethanolamine, decyldiethanolamine, triethanolamine, iso-sterolamine, etc.; )], inorganic test [for example: ammonia test metal hydroxide (hydrogen hydroxide, sodium hydroxide, gas oxidation clock, etc.), alkaline earth metal hydroxide (magnesium hydroxide, calcium hydroxide, etc.), alkali metal carbonate (1⁄4 acid, potassium carbonate, etc.)]. These bases can be used alone or Two or more kinds are used in combination. The neutralizing agent is added in an amount of from 4 to 12 equivalents (preferably 〇. 6 to 1 equivalent) per equivalent of the anionic group. ® Isocyanate-based terminal prepolymer obtained thereby a polyurethane prepolymer having two or more free isocyanate groups at the terminal of the molecule, and the content of the isocyanate group (isocyanate group content) is, for example, 〇3 to 1% by mass, preferably 0.5 to 6% by mass. 5〜且。 The average number of molecular weights of the isocyanate group is, for example, 1. 5~3. 〇, preferably 1. 9~2. The standard polystyrene is measured by GPC measurement of the calibration curve. The amount average molecular weight is, for example, 1 to 30000, preferably 1,500 to 20,000. Further, the hydrophilic group concentration of the isocyanate-based terminal prepolymer is, for example, 097143467 16 200932776 0. W. 0 surface 1/g, preferably 0. 2~G, 7 coffee 1/g, especially Q. 2~ Q. 6 moves i/g is better. In order to obtain the aqueous polyaminophthalic acid ester of the present invention, the heterocyclic S-based terminal prepolymer obtained as described above is then reacted with a chain extender. In the present invention, the 'chain extender may, for example, be a low molecular weight polyol, a polyamine or an amine alcohol. The low molecular weight polyol may, for example, be a low molecular weight polyol as described above.

Ο Polyamines include, for example, aromatic polyamines such as 4,4,~diphenylsulfonium diamine; or aromatic aliphatic groups such as 1'3- or 1,4-dimethylenediamine or mixtures thereof. An amine; or for example: 3-aminomethyl_3,5 5_trimethylcyclohexylamine (common name: isophor steel triamine) '4, 4' dicyclohexyl decyl diamine, 2, 5(2,6)-bis(aminomethyl)bicyclo[2·2.1]heptane l l__ or bis(aminomethyl)cyclohexane or mixtures thereof, 1,3- or丨, 4_cyclohexene diamine or a mixture of such alicyclic polyamines; or for example: ethylenediamine, hydrazine, 3-propanediamine, hydrazine, 4-butanediamine 1'6 /, methylene Aliphatic polyamines such as monoamines, hydrazine (including hydrates), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and the like. Further, the 'amine alcohol' may, for example, be N-(2-aminoethyl)ethanolamine or the like. Further, the chain extender may, for example, be an active hydrogen compound containing an alkoxyalkyl group. The active hydrogen compound containing an alkoxyalkyl group is a compound containing an alkoxyalkyl group and an active hydrogen group. Examples of the alkoxy group bonded to the Si atom and the alkoxy group bonded by the Si atom include: oxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group, isobutoxy group, etc. 097143467 17 200932776 Alkoxy group having 1 to 4 carbon atoms, etc., preferably decyloxy or ethoxy. Further, the number of bonds of the alkoxy group to the Si atom is usually 1 to 3, preferably 1 to 2. The active hydrogen group is an active hydrogen group which reacts with an isocyanate group, and may, for example, be an amine group, a hydroxyl group or the like, and is preferably an amine group. Such an active hydrogen compound containing an alkoxyalkyl group is, for example, represented by the following general formula (1): General formula (1): ❹[Chemical 2] 〇2 NH2—R4-NH-> R3*~Si- f OR1 )m (wherein R1 and R2 are the same or mutually different alkyl groups having 1 to 4 carbon atoms. R3 and R4 are the same or mutually different alkyl groups having 1 to 4 carbon atoms. m means In the above general formula (1), R1 and R2 may, for example, be an alkyl group having 1 to 4 carbon atoms such as an anthracenyl group, an ethyl group, a propyl group or a butyl group. Further, examples of R3 and R4 include an alkylene group having 1 to 4 carbon atoms such as an anthracenylene group, an exoethyl group, a propyl group, and a butyl group. The active hydrogen compound containing an alkoxyalkyl group, more specifically, for example, N-y5-(aminoethyl)-T-aminopropyl decyl decyloxy decane, \-cold- (Aminoethyl)-7-aminopropyltrimethoxy decane, 7-(2-aminoethyl)aminopropyltriethoxy pulverization, T_(2-aminoethyl)amine Base propyl decyloxy chopping, Τ-(2-aminoethyl)aminopropyl diethoxy carbamide, 7-aminopropyltrimethoxy decane, 7-aminopropyltriethyl Oxydecane, r-097143467 18 200932776 Aminopropyl dimethoxy decane, γ-aminopropyl diethoxy decane, N, N, _ bis [r-(trimethoxy decyl) propyl] Ethylenediamine and the like. Most preferred is N_々(aminoethyl)-r-aminopropylmercaptodimethoxydecane. Further, the concentration of the active hydrogen group contained in the 'chain elongation agent t is preferably from 250 to 800 mgKOH/g', more preferably from 350 to 600 mgKOH/g. When the concentration of the active hydrogen group is within this range, an aqueous polyurethane sulfonic acid resin excellent in durability can be obtained. 〇 These chain extenders may be used alone or in combination of two or more. Further, in these, it is preferred to use a polyamine together with an active hydrogen compound containing an alkoxyalkyl group. Further, in obtaining the aqueous polyaminophthalate resin of the present invention, the isocyanate-based terminal prepolymer obtained above is reacted with a chain extender in water and dispersed. Thereby, the aqueous polyamino phthalate resin which is obtained by chain-extending the isocyanate group-terminated prepolymer with a chain extender can be obtained in the form of an aqueous dispersion (dispersion). ❹ When the heterologous acid-based terminal prepolymer and the bond extender are reacted in water, for example, the isocyanate-based terminal prepolymer is first added to water to disperse the isocyanate-based terminal prepolymer. Next, a chain extender is added thereto, and the isocyanate group-terminated prepolymer is subjected to chain elongation. When the isocyanate g-based terminal prepolymer is dispersed, the isocyanate group-terminated prepolymer is slowly added to water under stirring. The water system is preferably added in an amount of from 60 to 1,000 parts by mass based on 100 parts by mass of the isobornyl group-terminated prepolymer. 097143467 19 200932776 Furthermore, in the isocyanate-based end prepolymer dispersed in water, the chain extender is used under the lining of the isocyanate-based chain of the prepolymer. The ratio of the active hydrogen group (hydroxyl group and the amine group, etc.) of the extender (active hydrogen group / cesium isocyanate) is, for example, a ratio of ◦ 5 to 1.1 (preferably Q. 7 to 1). Further, 'when the chain extender is a diamine (including a diamine containing an alkoxy group), the reactivity of the amine group with the isocyanate group of the isocyanate terminal prepolymer is high, and The intermolecular coagulation of the urea bond formed by the reaction (IV) is thus required to reduce the local reaction of the chain extender with the isocyanate monomer. Therefore, the chain extender is preferably formulated in the form of an aqueous solution or a solution. The concentration of the diamine in the aqueous solution or solution is preferably at least 2% by mass, particularly preferably at least 50% by mass. Further, the chain extender is preferably added at a temperature of 4 or less (rc), and after the addition is completed, stirring is further carried out, for example, at a normal temperature. Further, when the isocyanate group-terminated prepolymer is obtained by solution polymerization, After completion of the reaction of the isocyanate group-terminated prepolymer, the organic solvent is removed by heating at an appropriate temperature under, for example, a reduced pressure. The aqueous dispersion of the aqueous polyamine methyl ester resin obtained thereby is Depending on the solid content, it is prepared in a manner of, for example, 1 to 70% by mass (preferably 20 to 50% by mass). Further, the number average molecular weight of the aqueous polyurethane resin (based on standard polystyrene) The number average molecular weight measured by the GPC measurement of the measuring line is, for example, 3, 〇〇〇~1〇〇, 〇〇〇' preferably 5, 〇〇〇~80, 000. In addition, the aqueous polyurethane resin (solid part) is an amine ruthenium phthalate-to-urea-based feed 097143467 20 200932776 than 'for example, 〇, 〇 5~1. 2, especially 0. 1~0. 8 is better. When using an active compound containing an alkoxylated group In the case of the chain extender, the content of Si atoms in the aqueous polyurethane resin is, for example, 0.05 to 1.5% by mass, preferably 〇. 5 to 1.2% by mass, particularly 0. 07 to 0. 8 mass% is preferred. If the content of the si atom is in the above range, the isocyanate group of 1,4-bis(isocyanato-t-yl)cyclohexane is 50 moles relative to the total number of moles of the isocyanate group. An aqueous polyamine phthalate resin composed of a polyisocyanate® ester in a ratio of more than % is advantageous in that a coating film having improved mechanical stability and improved solvent resistance and softening temperature can be obtained.

The method for measuring the content of Si atoms is, for example, the distillation of the water contained in the aqueous polyamino phthalate resin. The film is formed into a film using an aqueous polyamine phthalate resin, and then the solid state high resolution NMR of the film is measured. Or the organic component of the film is completely dissolved by the wet ashing method (described later in the following [Example]), and then subjected to atomic absorption, ICp luminescence, and fluorescence ray ray method. Method of measurement. Among these, ICP luminescence analysis is preferred. Further, the aqueous polyurethane resin is, for example, determined to have a mechanical stability of 200 /ig/g or less, preferably 180/zg/g, according to the Maron test (described later in the following [Example]). Hereinafter, it is preferably 160#g/g or less. Therefore, when the aqueous polyurethane resin of the present invention is formed into a film, a coating film having excellent dispersion stability, solvent resistance, and heat resistance and excellent hand feeling can be obtained, and the aqueous polyurethane substrate of the present invention. The acid ester resin is suitable for artificial leather and synthetic leather which have the above characteristics. 097143467 200932776 In addition, the film formation system uses a known coating method such as a gravure coating method, a reverse coating method, a light coating method, a bar coating method, a spray coating method, an air knife coating method, or a dip coating method. The aqueous polyamino phthalate resin is applied to the substrate and then dried by heating. When the aqueous polyurethane sulfonic acid resin of the present invention is used in the production of artificial leather and synthetic leather, it can be used as a raw material such as a wet method or a dry method. Further, the aqueous polyurethane resin of the present invention is not limited to the above-mentioned artificial leather and synthetic leather, and can be used for various purposes such as automobiles, electronic equipment, clothing, medical materials, building materials, paints, and adhesives. . [Examples] Next, the present invention will be described based on the production examples, the synthesis examples, the examples, and the comparative examples. The present invention is not limited by the following examples. In addition, in the following descriptions, "parts" and "%" are quality standards unless otherwise stated. Further, the measurement methods used in the relevant synthesis examples and the like are as follows. (Hydrophilic group concentration/unit: mmol/g of the isocyanic acid-based terminal prepolymer) The hydrophilic group concentration of the hetero-acid vinegar-based terminal prepolymer is a potentiometric titration device (manufactured by Hiranuma Sangyo Co., Ltd., model: COM -980), according to the neutralization titration method. More specifically, about 1.5 g of the prepolymer solution before the addition of TEA was weighed and dissolved in a previously prepared 40 ml of a terpene/ethanol mixed solvent (toluene/ethanol volume ratio of 2/1). Next, potentiometric titration of the hydrophilic potassium (a reagent for titration) was measured using G·lmol/L ethanolic hydroxide 097143467 22 200932776. Further, in the hydrophilic group concentration, the hydrophilic group corresponds to a carboxyl group in the isocyanate-terminated prepolymer. Further, since the sample was measured as an acetonitrile solution of the prepolymer, the amount of f of the prepolymer was corrected based on the loaded solvent, and the hydrophilicity of the prepolymer was calculated from the measured value. ° ❹ ❹ (oxyethylene concentration/unit: mass% of the end of the isocyanate s-group (tetra)) In the isocyanate end-polymer of 0.5 g, the internal standard substance was used. Tetrachloroethane dissolved in the hydrogenated gas imitation was added in a certain amount, and further hydrogenated chloroform was added to make the total volume 5 mL. The oxyethylene group concentration was determined by measurement of the solution w 1H__, JNM-AL400). (Isocyanate shouting end of the county inspection content containing cyanide _ base content / unit: mass%) Iso-cyanide end of the county solution is different from the purpose of the base content using the potential difference device, using the two according to m κ_1556 The amine method was used for the measurement. Production Example 1 (Manufacturing method of 1,4-bis(isocyanatomethyl)cyclohexane) The trans form measured by 13c-_ is determined to be a bis(amino fluorenyl) ring The chilled (manufactured by Mitsubishi Gas Chemical Co., Ltd.) is used as a raw material, and the hot and cold two-stage phosgene method is carried out under normal pressure. Namely, 'the flask was attached: a mixing rod, a thermometer, a phosgene introduction tube, a dot 097143467 23 200932776 dropping funnel and a cooling tube, and the flask was filled with 400 parts by mass of o-dichlorobenzene. While the flask was cooled by cold water, the temperature in the flask was set to 10 ° C or lower, and 280 parts by mass of phosgene was introduced through the phosgene introduction tube. A mixture of 1 part by mass of 1,4-bis(aminomercapto)cyclohexane and 500 parts by mass of o-dichlorobenzene was placed in a dropping funnel, and the mixture was added to the flask over 3 minutes. . During this time, the temperature inside the flask was maintained below 3 °C. After the addition was completed, a white paddle liquid was present in the flask. Further, while introducing helium gas, the reaction temperature was raised to 150 ° C, and the reaction was continued at 150 ° C for 5 hours. The reaction solution in the flask will be a pale brown clear liquid. After the reaction is completed, degassing is carried out according to 10 (M50 ° C, nitrogen gas is ventilated at 10 L/h. The solvent is distilled off with o-dichlorobenzene under reduced pressure, and further decompressed under reduced pressure, taking a boiling point of 138 to 140 A fraction of °C/0. 7 KPa. Thus, 123 parts by mass of 1,4-bis(isocyanatononyl)cyclohexane (color yield 90%) of a colorless transparent liquid was obtained. 4-bis(isocyanatomethyl)cyclohexane was determined according to the gas chromatograph analyzer, and the purity was 99.9%, and the hue system 5 was determined by APHA measurement, and measured by 13C-NMR measurement. The trans/cis ratio is 93/7. Production Example 2 (Synthesis of a diol containing a polyoxyethylene side chain) • Filling a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube 1 part by mass of methoxypolyethylene glycol having a number average molecular weight of 1000 (manufactured by Toho Chemical Industry Co., Ltd.) and 1,6-hexamethylenediamine 097143467 24 200932776 isocyanate (trade name: TAKEMTE -700 ' MITSUI 1682 parts by mass of CHEMICALS POLYURETHANES Co., Ltd., reacted at 90 ° C for 9 hours under nitrogen atmosphere. The reaction solution is subjected to thin film distillation, and unreacted 1,6-hexamethylene diisocyanate is removed to obtain a polyoxyethylene group-containing monoisocyanate, followed by a mixer, a thermometer, a reflux tube, and a nitrogen introduction tube. In a four-necked flask, 82.5 parts by mass of diethanolamine was charged. In a nitrogen atmosphere, 917.5 parts by mass of the polyoxyethylene alkenyl group-containing monoisocyanate was air-cooled, and the reaction temperature was not dripped more than 70 ° C. After the completion of the dropping, in a nitrogen atmosphere, stirring was carried out for 7 hours according to 7 (TC), and it was confirmed that the isocyanate group disappeared to obtain a diol containing a polyoxyethylene side chain. In the diol containing a polyoxyethylene side chain The oxyethylene group concentration was 76% by mass as measured by iH_NMR. Synthesis Example 1 (Synthesis of a hydrophilic group-containing prepolymer solution (A)) Four having a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube In the mouth-shaped flask, 780 parts by mass of 1&4; bis(isocyanatoinyl)cyclohexyl (hereinafter referred to as "1,4-BIC") of the following 1 to 4, 1 production example 1 was charged; 2 in advance Heated to 110 ° C And an amorphous polycarbonate fuel (manufactured by T-5652, manufactured by Asahi Kasei Chemicals Co., Ltd.) having a number average molecular weight of 2,000 parts by weight, and 3000 parts by weight; 3 acetonitrile (hereinafter referred to as "AN") 1000 mass 4' is heated as in the case of amorphous polycarbonate diol, and 220 parts by mass of dimercaptopropionic acid (hereinafter referred to as "DMPA") dried under reduced pressure. Then, under the environment of nitrogen 097143467 25 200932776 The reaction was carried out at 75 ° C for 8 hours. Thus, a solution of an isocyanate group-terminated prepolymer (hereinafter referred to as "prepolymer") having an isocyanate group content of 1.40% by mass was obtained. Next, the reaction liquid was cooled to 2 (TC, and 158 parts by mass of triethylamine (hereinafter referred to as "TEA") was added. That is, it became 0 with respect to the hydrophilic group (rebel) in the isocyanate-based terminal prepolymer. 95 equivalents were added. Then, the mixture was stirred and mixed for 30 minutes at the same temperature to obtain a hydrophilic group-containing isocyanate-based terminal prepolymer which was neutralized with tea hydrazine (hereinafter referred to as "hydrophilic group-containing prepolymer". ") Solution (A). Details of the synthesis conditions and properties of the obtained hydrophilic group-containing prepolymer solution (A) are shown in Table 另外. In addition, in Table 1, the "equivalent ratio of isocyanate groups" means The equivalent ratio of the isocyanate g group of the polyisocyanate to the base of the polyhydric alcohol and the active hydrogen compound containing a hydrophilic group. Synthesis Example 2 (Precipitate solution containing a hydrophilic group (B) Synthesis) ❹ In addition to changing HWC to 950 parts by mass, change AN to 1〇45 parts by mass, DMPA to 230 parts by mass, and TEA to 165 parts by mass, the rest are the same as in synthesis example i The operation, the content of the iso-acid vinegar base content of 2.65 mass% containing the pro Prepolymer solution (8). Details of the synthesis conditions and properties of the obtained hydrophilic group-containing prepolymer solution (8), as shown in the following. Synthesis Example 3 (synthesis of hydrophilic group-containing prepolymer solution (c)) In addition to changing 1,4-BIC to · parts by mass, changing AN to iiu parts by mass, changing MPA to 244 parts by mass, and changing TM to π parts by mass, 097143467 26 200932776 is the same as in Synthesis Example 1. The operation is carried out to obtain a hydrophilic group-containing prepolymer solution (〇) having an isocyanate group content of 4.23 mass%. Details of the synthesis conditions and properties of the obtained hydrophilic group-containing prepolymer solution (C), as shown in the table Synthesis Example 4 (Synthesis of a hydrophilic group-containing prepolymer solution (£>)) In addition to changing 1' 4-BIC to 1500 parts by mass, the AN was changed to 1190 parts by mass, and the DMPA was changed to 260 mass. In the same manner as in the synthesis example, the hydrophilic group-containing prepolymer solution (D) having an isocyanate group content of β 5.96 mass% was obtained, except that the TEA was changed to 186 parts by mass. Hydrophilic prepolymer; details of the synthesis conditions and properties of the trough (D), as shown in Table 1. Example 5 (Synthesis of a hydrophilic group-containing prepolymer solution) In addition to changing 1,3-bis(isocyanatomethyl)cyclohexane (trade name: Li Yin "1,3-BIC") 950 parts by mass, ❹ Τ-600, manufactured by MITSUI CHEMICALS POLYURETHANES (the following simple 'change AN to 1045 parts by mass,

I soil, ~ 7 only Liu Liu Jing. The details of the synthesis conditions and properties of the prepolymer solution (8), as shown in Table 土. Synthesis Example 6 (synthesis of hydrophilic group-containing prepolymer solution (F)) ', and changing 1,4-BIC to 523 '', DMPA was changed to 230 mass, and the rest were as in Synthesis Example 1 except that 1' 3 -BIC was changed to 428 parts by mass, and the quality was injured. The AN was changed to 1 〇 45 parts by mass, and the TEA was changed to 165 parts by mass. The same operation of 097143467 27 200932776 resulted in an isocyanate group content of 2.69 mass%. A hydrophilic group-containing prepolymer solution (F). The details and properties of the synthetic conditions of the hydrophilic group-containing prepolymer solution (F) obtained are shown in Table 1. Synthesis Example 7 (Synthesis of a hydrophilic group-containing prepolymer solution (ς))

In addition to changing the isophoric acid (IPDI, trade name: VESTANAT IPDI, DEGUSSA company) to 116 parts by mass, change an to u〇5 quality injury, change DMPA to 260 parts by mass, The TEA was changed to 186 parts by mass. The remainder was prepared in the same manner as in Synthesis Example 1, to obtain a hydrophilic group-containing prepolymer solution (〇) having an isocyanate group of 2.68 % by mass. The details and properties of the synthesis conditions of the obtained hydrophilic group-containing prepolymer solution (G) are shown in Table 1. Synthesis Example 8 (Synthesis of a hydrophilic group-containing prepolymer solution (η)) In addition to 4,4'-methylene bis(cyclohexyl isocyanate) (trade name: VESTANAT MDI, manufactured by DEGUSSA) (hereinafter referred to as "Hi2MM") ” 〇❷ 〇❷ mass parts, change AN to 1158 parts by mass, change DMPA to 260 parts by mass, change TEA to 186 parts by mass, and use the same operation as in the synthesis example to obtain isocyanate group content. 2. 54% by mass of a hydrophilic group-containing prepolymer solution (H). The details and properties of the synthesis conditions of the hydrophilic group-containing prepolymer solution (H) obtained are shown in Table 1. — Synthesis Example 9 (Synthesis of a hydrophilic group-containing prepolymer solution (!)) • In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 4,4'-methylene double was charged. (cyclohexyl isocyanate) 〇 {1 sprinkle 1) 1) 129 mass 097143467 28 200932776 parts, amorphous polycarbonate diol (trade name: τ_5652) 3 parts by mass, AN (1054 parts by mass) and DMPA ( 232 parts by mass), after reacting for 3 hours at 75 ° C in a nitrogen atmosphere, '丨, 4-bic (856 parts by mass) was added, and the reaction was further carried out for 6 hours at the same temperature. Thereby, a prepolymer solution having an isocyanate group content of 2.65 mass% was obtained. Next, the reaction liquid was cooled to 2 (TC, and hydrazine (16 Å by mass) was added. That is, TEA was added to the hydrazine group (carboxyl group) in the isocyanate-based prepolymer so as to be 95 eq. Then, stirring and mixing were carried out for 3 minutes at the same temperature to obtain a hydrophilic group-containing prepolymer solution (I) neutralized with a few acids by TEA. Synthesis conditions of the hydrophilic group-containing prepolymer solution (I) obtained And the properties are shown in Table 1. Synthesis Example 1 (Synthesis of Prepolymer Solution (J)) In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, the following 1 to 1 was placed. 5,11,4-BIC (447 parts by mass); 2 preheated © 110 ° C, and subjected to vacuum drying and amorphous polycarbonate diol having a number average molecular weight of 2000 (trade name: T-5652 'Asahi Kasei Chemical Co., Ltd.) 3000 parts by mass; 3ANC 1452 parts by mass); 4 acetone (1815 parts by mass); 5 as the amorphous polycarbonate diol is heated and subjected to vacuum drying to contain polyoxyethylene side chains 389 parts by mass of the diol. Then, the reaction was carried out for 7 hours at 75 ° C under a nitrogen atmosphere. Thus, a prepolymer solution (J) having an isocyanate content of 〇. 57% by mass was obtained. The details and properties of the synthesis conditions of the obtained prepolymer solution (J) are shown in Table 1. 097143467 29 200932776 Synthesis Example 11 (Synthesis of Prepolymer Solution (K)) In addition to changing 1,4-BIC to 496 parts by mass, AN was changed to 1473 parts by mass, and acetone was changed to 1841 parts by mass to contain polyoxygen. The prepolymer solution (K) having an isocyanate group content of 0.81% by mass was prepared in the same manner as in Synthesis Example 10 except that the diol of the ethylene side chain was changed to 394 parts by mass. The details and properties of the synthesis conditions of the obtained prepolymer solution (K) are shown in Table 1. Synthesis Example 12 (Synthesis of Prepolymer Solution (1)) ❹ In addition to changing 1,4-BIC to 799 parts by mass, 'AN was changed to 1600 parts by mass, and acetone was changed to 2001 parts by mass, and the polyoxyethylene side was contained. The prepolymer solution (L) having an isocyanate group content of 2.35 mass% was obtained in the same manner as in the synthesis example 1 except that the diol of the chain was changed to 428 parts by mass. The details and properties of the synthesis conditions of the obtained prepolymer solution (L) are shown in Table 。. Synthesis Example 13 (Synthesis of Prepolymer Solution) In addition to changing Hl2MDI to 676 parts by mass, AN was changed to 1548 parts by mass, © acetone was changed to 1936 parts by mass, and diol containing polyoxyethylene side chain was changed to 414. Except for the Bailey portion, the prepolymer solution having the isocyanate group content of 〇8% by mass (M> the prepolymer solution (M) obtained in the same manner as in Synthesis Example 1 was prepared and the details of the synthesis conditions and Traits, as shown in the table. 097143467 30 200932776 ο 〔1<〕 co g $ Ί SBu οοοε 00 wear

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M s^st^ (H0/03N)f4^峒驷宕硪峒驷宕硪潜佑 (%¥輙)_秘硪爱 lo^s荽铋羝c_i) 卜93| 200932776 Example 1 (Aqueous polyamine hydrazine (Synthesis of the ester resin (A)) 1000 parts by mass of ion-exchanged water adjusted to 10 ° C in advance was placed in a stainless steel container of 3 L volume, and a homogenizer (trade name: K. HOMO DISPER, manufactured by PRIMIX Co., Ltd.) was used. Under stirring at 2000 rpm, 500 parts by mass of the hydrophilic group-containing prepolymer solution (A) adjusted in advance at 20 ° C was slowly added and dispersed. Next, 3.85 parts by mass of hydrazine was prepared into a chain extension of a 20% by mass aqueous solution, 19.2 parts by mass of the long-range liquid, and was added while paying attention to heat generation. Further, the equivalent ratio of the amine group in the chain extender to the isocyanate group in the prepolymer (hereinafter referred to as "chain extender equivalent ratio") is 〇. 95. In addition, the hydrazine-based hydrazine monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) "the mass fraction of hydrazine" corresponds to hydrazine monohydrate (in the following examples and comparative examples, The chain extender equivalent ratio and the amount of hydrazine used are also the same. Then, after the chain extender liquid was added, it was subjected to a chain elongation reaction by performing 2 hours at 25 ° C for 2 hours. Then, the crucible was distilled off under reduced pressure to obtain an aqueous dispersion of an aqueous polyaminophthalic acid resin (Α) having a solid content of 35% by mass. The details and properties of the synthetic conditions of the obtained aqueous polyurethane oxime resin (Α) are shown in Table 2. The amount of the hydrazine is 5.82 parts by mass and the hydrazine is used in combination with the hydrazine-containing prepolymer solution (Β). -々(Aminoethyl)_τ_aminopropylmethyldioxime 097143467 32 200932776 Oxygen Shiki (trade name: KBM6G2 Shin-Etsu Chemical Co., Ltd.,

The Si atom 3 is in an amount of 13.6% by mass) 6 parts by mass, and is prepared in an amount of 2% by mass of the chain extender liquid of the aqueous solution of 59.1 parts by mass, and the rest are in accordance with the same conditions and operations as in the first embodiment. An aqueous dispersion of an aqueous polyurethane resin (B). The synthesis conditions and properties of the obtained aqueous polyurethane resin (8) are shown in Table 2. Example 3 (Synthesis of aqueous polyamino phthalate resin (c)) The use of a hydrophilic group-containing prepolymer solution (8) is used, and the bond elongating agent is used to prepare 2.7 parts by mass of hydrazine to 20 f. An aqueous dispersion of aqueous polysilicic acid lysate «:) was prepared according to the same conditions and operation as in the case of m, except for the chain extender liquid %· & Details of the synthesis conditions and properties of the obtained aqueous polyamino phthalate resin (C) are shown in Table 2. Example 4 (Synthesis of aqueous polyamino phthalate resin (D)) ® a base prepolymer solution (B), and the chain extender is prepared by using N-/5 (aminoethyl)-r-aminopropyl fluorenyl dimethoxy oxalate (KBM602) in an amount of 30.0 parts by mass. An aqueous dispersion of the aqueous polyaminophthalic acid ester resin (D) was prepared in the same manner as in Example 1 except that the chain extender liquid of the 20% by mass aqueous solution was 149.9 parts by mass. The details and properties of the synthesis conditions of the obtained aqueous polyurethane oxime resin (D) are shown in Table 2. 6质量质量调整。 The hydrazine-based prepolymer solution (c), and the chain extender is adjusted to use hydrazine 11.6 parts by weight An aqueous dispersion of the aqueous polyurethane resin (E) was prepared in the same manner and operation as in Example 之外 except that the chain extender liquid of a 20% by mass aqueous solution was 58 parts by mass. Details of the synthesis conditions and properties of the obtained aqueous polyurethane oxime resin (E), as shown in Table 2, Example 6 (synthesis of aqueous polyamine phthalate resin (F)) ® except for using a hydrophilic group The prepolymer solution (D), and the chain extender used is 4.91 parts by mass of hydrazine with Ny?(aminoethyl)-γ-aminopropyl fluorenyl-methoxy oxane (KBM602H7.2 mass) An aqueous dispersion of an aqueous polyurethane resin (F) was prepared according to the same conditions and operation as in Example ', except that the chain extender liquid was prepared to have a 20% by mass aqueous solution of 260. 5 parts by mass. The synthesis conditions of the obtained aqueous polyamino phthalate resin (F) are shown in detail in & and the properties are shown in Table 2. ® Example 7 (Synthesis of aqueous polyurethane resin (G)) The hydrophilic group-containing prepolymer solution (D) was used, and the chain was elongated; 16.4 parts by mass of the hydrazine-linked ammonia was prepared into a 20% by mass aqueous solution of the chain extender liquid of 81 8 parts by mass, and the rest were as in the examples. 1 The same conditions and operation were carried out to prepare an aqueous dispersion of the aqueous polyurethane resin (G). The details and properties of the synthesis conditions of the phthalic acid ester resin (G) are shown in Table 2. Example 8 (Synthesis of Aqueous Polyurethane Resin (H)) 097143467 34 200932776 In addition to the use of hydrophilic groups The prepolymer solution (1), and the chain extender was used in the same manner as in Example 丨 except that the chain extender was prepared by dissolving 7.27 parts by mass of hydrazine into a 20% by mass aqueous solution. And an operation, the aqueous dispersion of the aqueous polyamino phthalic acid vinegar resin (H) was obtained. The details and properties of the synthesis conditions of the obtained aqueous polyurethane resin (H) are shown in the table. 9 (Synthesis of aqueous polyamino phthalate resin ())) The prepolymer solution synthesized in Synthesis Example 10 was placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube ( j) 5〇〇g, and warmed to 30 C. The receiver 'slowly added 85 〇g of ion-exchanged water pre-adjusted to 20 ° C and watered' in the addition of hexamethylene diamine (Wako Pure Chemical Industries) Co., Ltd.'s 'hereinafter referred to as "HDA") 0.85 parts by mass and N-call (amino group) (6)-Aminopropylmethyldimethoxy decane (KBM602) 5. 06 parts by mass of a chain extender liquid prepared as a 20% by mass aqueous solution, 29.6 parts by mass, and a bond extension length. Then 'in the chain After the addition of the elongation agent liquid, the chain extension reaction was carried out by performing the mixture for 2 hours at 10 to 25 ° C. Then, AN and acetone were removed under reduced pressure to obtain an aqueous polyamine group having a solid content of 35% by mass. An aqueous dispersion of the phthalate resin (I). The synthesis conditions of the obtained aqueous polyamino phthalate resin (I) are as follows in detail, as shown in Table 3. • Example 10 (aqueous polyurethane) Synthesis of phthalate resin (J)) In addition to the use of the prepolymer solution (K), and the chain extender is used, HDA (2.4 mass 097143467 35 200932776 parts) and N-yS (aminoethyl)- τ-Aminopropyl decyl decyloxy oxime (ΚΒΜ 602) 5. 09 parts by mass of a chain extender prepared to be a 20% by mass aqueous solution is expanded by 37. 4 parts by mass, and the rest are the same as in Example 9. Conditions and operation, an aqueous dispersion of an aqueous polyamino phthalate resin (J) was obtained. The details and properties of the synthesis conditions of the obtained aqueous polyurethane resin (J) are shown in Table 3. Example 11 (Synthesis of aqueous polyamino phthalate resin (Κ)) β except that the prepolymer solution (L) was used, and the chain extender used was 3 parts by mass of RDAC1z) and N-cold (aminoethyl group) -r-aminopropylmethyldimethoxy decane (KBM602) 5.28 parts by mass of a chain extender liquid prepared in a 20% by mass aqueous solution of 87. 9 parts by mass, the same conditions as in Example 9 And an operation, an aqueous dispersion of an aqueous polyamino phthalate resin (κ) was prepared. The details and properties of the synthesis conditions of the obtained aqueous polyurethane resin (Κ) are shown in Table 3. ® Comparative Example 1 (Synthesis of Aqueous Polyurethane Resin (L)) In addition to the use of a hydrophilic group-containing prepolymer solution (£), and the chain extender used 7.5 parts by mass of hydrazine and hydrazine - Lu (aminoethyl)_r_aminopropylmethyldimethoxycarbazide)αΒΜ602)5. 93 parts by mass of a bond prepared as a 2% by mass aqueous solution, 58.4 parts by mass of the extender liquid, An aqueous dispersion-liquid of aqueous (10) ketone-resin a) was obtained in accordance with the same procedure and operation as in Example i. The obtained aqueous polyurethane--(details and properties of the synthesis conditions of 1 ') are shown in Table 2. 097143467 200932776 Comparative Example 2 (Synthesis of aqueous polyamino phthalate resin (Μ)) In addition to the use of hydrophilic groups The prepolymer solution (F), and the chain extender is prepared according to the same conditions as in Example 1 except that 3.8 parts by mass of hydrazine is prepared as a chain extender liquid % by mass of a 20% by mass aqueous solution. The aqueous dispersion of the aqueous polyurethane resin is prepared by the operation. The details and properties of the synthesis conditions of the aqueous polyurethane resin (〜) from ~μ' are shown in Table 2. Comparative Example 3 (Synthesis of aqueous polyamino phthalate resin (Ν)) In addition to the use of a hydrophilic group-containing prepolymer solution (G), and the chain extender used N-dots (aminoethyl)-γ - aminopropyl decyl dimethoxy decane (KBM6_G. 2 parts by mass prepared as a chain extender liquid of 2 g% by mass aqueous solution, 151.1 parts by mass, the same according to the same conditions and operation as in Example 制Aqueous dispersion of aqueous polyaminocarbamate-lipid (8). Aqueous polyamine phthalate tree obtained The details and properties of the synthesis conditions of the lipid (N) are shown in Table 2. Comparative Example 4 (Synthesis of Aqueous Polyurethane Resin (〇)) Shouting with a Hydrophilic Group (8) 1 Chain Elongation _ Use N. The aqueous dispersion of the aqueous polyaminocarbamic acid S oxime resin (0) was obtained in the same manner as in the above examples, and the synthetic conditions of the obtained aqueous polyurethane carboxylic acid resin (0) were detailed. Time and traits, as shown in Table 2. 097143467 37 200932776 Comparative Example 5 (Synthesis of aqueous polyamino phthalate resin (p)) In addition to the use of prepolymer solution (8), and chain elongation _ use legs (2 · 35 (parts by mass) with hydrazine-bromoethyl)aminopropylmethyldimethoxyxanthine. (Na 02) 5. 10 parts by mass of a bond extender prepared as a 2% by mass aqueous solution • Liquid 37·3 An aqueous dispersion of the aqueous polyamine-based resin (ρ) was prepared in the same manner and operation as in Example 9 except for the quality of the tube. The details and properties of the synthesis conditions of the obtained aqueous polyurethane carboxylic acid resin (8) are shown in Table 3. [Physical property evaluation] The Si atom concentration, mechanical recording, oil resistance, and fracture of the aqueous polyurethane urethane resin (hereinafter referred to as "each aqueous polyurethane vinegar resin") obtained in accordance with each of the examples and the respective ratios The stretching, softening temperature, hand feeling and touch were measured in accordance with the following methods. The results are shown in Table 2. <Preparation of test sample> ❹ [Examples 1 to 8 and Comparative Example 4] Each aqueous polyurethane resin was applied onto an 0HP film which had been degreased with acetone using an applicator. The film was dried in accordance with U (rc) for 1 hour to obtain a film having a thickness of about 60/inch. The film was then aged in a laboratory at a humidity of 55% with respect to humidity for 1 week. Test samples were prepared therefrom. [Examples 9 to 11 and Comparative Example 5] Each of the aqueous polyamine hydrazines was plasticized, and the saturated water vapor of 9 〇Ό or more was boiled for about 1 minute to be solidified. The relative fishing degree was 097,143,467. 38 200932776 55% of the laboratory was allowed to stand for one night and then dried for 1 hour at 11 °c to obtain a thin enamel with a thickness of about 250. Then, the film was made in a laboratory of μιη, 55% relative humidity. 】The aging of the week ^The test sample is prepared accordingly. <Si atom concentration (unit: mass%)> . Wet ashing method using nitric acid and sulfuric acid (for example, refer to "Analytical Chemistry Handbook", editor: Corporate Legal Person Japan Analytical Chemistry Association, Publisher: Maruzen Co., Ltd., Heisei 3 years 1 Published on January 30, p. 1292, the organic components of each of the aqueous polyaminophthalate test samples are completely decomposed and heated to obtain a dry solid. Next, a powder shape is added to the dried solid. Sodium carbonate is further heated to melt the solid solid in the molten salt of sodium carbonate. Then, it is left to cool, and after solidification, the diluted hydrochloric acid is slowly added until it is weakly acidic, thereby preparing an analytical sample. (For example, refer to the "Analytical Chemistry Handbook", edited by: Japan Society of Analytical Chemistry, Publishing House: Maruzen Co., Ltd., published on November 30, 2003, pp. 265-266). ICP luminescence analyzer (icP-AES,

The Si atom concentration in each of the aqueous polyamine phthalate resins was measured by Seiko Instruments Co., Ltd. model: VISTA-PRO. Further, "n.d." in Table 2 means that since there is no Si atom, "there is no measured value. • [Mechanical stability: Maron test (unit: yg/g)> A test solution of each aqueous polyurethane 097143467 39 200932776 urethane resin aqueous dispersion diluted with ion-exchanged water and having a solid content of 5% by mass, After passing through the #300 mesh t-web, the resin remaining on the metal _ sieve was measured by a special cup for the mechanical stability test. Next, shearing (Maron test) was applied for 20 minutes under the conditions of a load of 147 N (15 kgf) and a number of revolutions of 1000 rpm using a Maron-type mechanical stability tester (manufactured by Rigaku Corporation). Next, the resin after the test was dried using a #300 mesh metal mesh, and the metal mesh was dried at 110 ° C for 1 hour. The mass of the metal mesh before and after the Maron test was measured, and the quality of the resin remaining in the metal mesh was measured. The measured masses were each converted to the amount of residual resin per solid fraction of the aqueous polyamine phthalate resin on the metal mesh screen. <Oil resistance acidity (unit: °/〇> The test sample of each aqueous polyurethane resin was cut into a size of lxi0 cm, and the quality of the test sample was measured. Then, it was immersed in oleic acid® at 23t 7 After the impregnation, the oleic acid adhered on the surface of the test sample is wiped off before the quality of the test sample is determined. Then the mass of the test sample after the impregnation is measured. From the test before and after immersion in oleic acid According to the following formula, the oil resistance acidity (%) is calculated. Oil resistance acidity (%) = (test sample mass after impregnation (g)_test sample mass before dipping (g)) / test before impregnation Sample quality X1 00 <softening temperature (unit: ° C)> A test sample of each aqueous polyurethane resin was punched into a 097143467 40 200932776 by a dumbbell to have a width of 5 mm and a length of 50 mm. Then 'the test sample Using a dynamic viscoelasticity measuring device (manufactured by IT Measurement and Control Co., Ltd., model: DVA_2〇〇), test samples were prepared according to the stretching mode, the length between the marking lines of 25 mm, the heating rate of 5 °C/min, and the measurement frequency of 10 Hz. Dynamic viscoelastic In the turning area where the elastic modulus of the flat area of rubber or leather is present, the intersection of each tangent of the elastic modulus is obtained, and the temperature is defined as the softening temperature. <Stretching elongation (EL) (Unit: % > ® A test sample of each aqueous polyamino phthalate resin was punched into a width of 1 cm and a length of l〇cm by using a bell. Then, a tensile compression tester (manufactured by INTESC Corporation) was used for the test sample. Model 205N), tensile test was carried out under conditions of 23 ° C, a tensile speed of 300 mm/min, and a distance between grippers of 50 mm, whereby the tensile elongation (EL) of each aqueous polyamine phthalate resin was measured. ;Feeling> The viscous (stickiness) and touch of each aqueous polyurethane resin test sample were evaluated by palpation according to the following evaluation criteria, and the results were based on the following evaluation criteria. Evaluation of the hand feeling. (Feel) 〇: Viscosity and touch are all 〇. △: Viscosity is 〇, touch is △ X: Viscosity, touch is either X. - (viscous Evaluation criteria) 〇: No stickiness occurred. 097143467 41 200932776 △: Only some Viscosity is slightly observed. X: Viscosity is present. (Evaluation criteria for tactile sensation) 〇: soft touch. △: slight residual marks when bent. X: Significant residual marks when bent.

097143467 42 200932776 10 Comparison K Ο SC § LO 1000 1 Divination <>α 143.5 1—<<〇§ r*H cva 05 i—H OO <N1 X 〇X Comparative Example 3 Geisha 〇> LT3 1000 1 OJ I1··( LT5 τ—Η 0.95 _1 Ο <=> I < in C<l § CD X 〇X Comparative Example 2 LO 1000 7.38 1 36.9 d CZ5 C<IL〇CO lH 05 <=? CO X < X Comparative Example 1 〇ω <=> LO 1000 5.75 5. 93 inch 〇〇LO 0.20 s CO LTD CO s CO XX 〇Example 8 <〇LO 1000 1__ 7 27 1 36.4 "dd TH OO CJ5 H LO OO CO 〇〇〇Example 7 〇Ο Ci <=> LO 1000 CO 1 i 1 OO S3 d LQ 05 TinH 卜 o <ΝΪ Another CO < 〇 <Example 6 Ο Ci 〇> LO 1000 1 < 03 47.2 260.5 1.42 § OO CNI § CvJ < 〇 < Example 5 W o 〇 <=> LO 1000 CO 1 < ι··Η 1 ◦ od LO dgt 1 < ΙΟ s <33 LO CO 〇〇〇 Example 4 o PQ <=> LT5 1000 1 〇149.9 0.95 § LO OO C<io CO CO 〇〇〇Example 3 〇CD PO <=> LO 1000 1____- . _____ - Bu·· 1 36.4 nd d CD Oa 1 < OO LO 03 o 〇〇〇 Example 2 OQ ◦ DQ O LO 1000 5. 82 6.00 CT5 0.20 § CO < N1 1 - H CNJ o OO CO 〇〇〇 Example 1 〇CO LO 1000 3.85 1 Oi r_H d § cn OO OO g Hydrophobic polyamino phthalate resin prepolymer solution (parts by mass) Ion-exchanged water (parts by mass) Hydrazine (parts by mass) KBM-602C parts by mass) 5 φ| ύ w Ul^ Si atomic concentration (mass? 〇 mechanical stability: Maron test (//g/g) Acidic acidity (%) Softening temperature (°c) Fracture tensile EL (%) Tactile evaluation Viscosity evaluation Tactile evaluation Bond Elongation Agent 20 Mass Physical Property Evaluation 200932776 [Table 3] Example 9 Example 10 Example 11 Comparative Example 5 Aqueous Polyurethane Resin IJKP Prepolymer Solution JKL Μ (mass) 500 500 500 500 Ion-exchanged water (Parts by mass) 850 850 850 850 Chain extender HDA (mass parts) 0. 85 2. 40 12. 3 2. 35 KBM-602C parts by mass) 5. 06 5. 09 5. 28 5. 10 20% by mass chain Aqueous solution of an extender (parts by mass) 29. 6 37. 4 87. 9 37. 3 Si atomic concentration (% by mass) 0. 25 0. 25 0. 25 0. 25 Mechanical safety Properties: Maron test (β g / g) 25 18 16 15 Oil resistance acidity (%) 21. 8 18. 7 16. 0 29. 2 Physical property evaluation Softening temperature (°C) 202 210 214 199 Breaking stretch EL (°/ 550) 550 500 380 460 Handle Evaluation 〇〇〇 Δ Viscosity Evaluation 〇〇〇〇 Tactile Evaluation 〇〇 Δ Δ In addition, the above description is provided in accordance with the exemplified embodiments of the present invention, but it is merely exemplary and may not be Limited interpretation. Variations of the invention that are readily apparent to those skilled in the art are covered by the scope of the appended claims. (Industrial Applicability) The aqueous polyurethane resin of the present invention is suitable for providing a coating film, artificial and synthetic leather. 44 097143467

Claims (1)

200932776 VII. Scope of application: 1. An aqueous polyurethane resin obtained by reacting the following isocyanate-based bundle prepolymer with a chain extender: at least 丨, 4-double (different The acid of the isocyanate group of ( lcocyanato)-methyl)cyclohexane is contained in a ratio of 50 mol% or more relative to the total number of moles of the iso-ester group. * ^ κ well acid ester, high molecular weight A polyol and an active hydrogen compound containing a hydrophilic group are obtained by carrying out a reaction. 2. The aqueous polyaminophthalate resin according to claim 1, wherein the above bond extender comprises an active argon compound having an alkoxyalkyl group. 3. The aqueous polyamino phthalate resin according to claim 1, wherein the Si atom is contained in an amount of from 0.05 to 1.5% by mass. 4. The aqueous polyurethane resin according to claim 2, wherein the above chain extender is a compound represented by the following general formula (1); general formula (1): ® [Chemical 1] NH2 -~R4-.MH—R3-Si-^〇R^ J (wherein R1 and R2 refer to the same or mutually different carbon number 4 alkyl; R3& R4 means the same or different carbon number 1 to 4 alkylene; m is an integer from 1 to 3). 5. The aqueous polyamine phthalate resin according to claim 1, wherein the '1'4-bis(isocyanatoinyl)cyclohexane system contains trans- 丨-bis(isocyanocyanate). The acid sulfhydryl group cyclohexane is 50% by mass or more. 097143467 45 200932776 , 6. A coating film obtained by the aqueous polyamine phthalic acid resin of the first application of the patent scope. 7. An artificial and synthetic leather, which is an aqueous polyurethane resin of the first application of the patent scope. 097143467 46 200932776 t IV. Designation of representative drawings: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. : [Chemical 1] NH2—R4-NH-R3-Si-f〇R1 )m 097143467 2