JP2017137591A - Method for producing coagulum - Google Patents

Abstract

A problem to be solved by the present invention is to provide a production method capable of coagulating an aqueous urethane resin composition without using a metal salt and obtaining a laminate having excellent texture. The present invention immerses a fiber substrate in a coagulation bath (x) containing an alcohol solvent (i) having 2 to 6 carbon atoms and not containing a metal salt (ii); Production of a coagulum characterized by being immersed in an aqueous urethane resin composition (y) containing an anionic urethane resin (A) having an aromatic ring, a nonionic emulsifier (B), and an aqueous medium (C) A method is provided. As the alcohol solvent (i), 2-propanol is preferably used. [Selection figure] None

Description

  The present invention relates to a method for producing a coagulum that can be suitably used for producing gloves.

  An aqueous urethane resin composition in which a urethane resin is dispersed in an aqueous medium can reduce the burden on the environment as compared to conventional organic solvent-based urethane resin compositions, so industrial gloves, artificial leather, synthetic leather, etc. In recent years, it has been used favorably as a material for producing leather-like sheets, coating agents, adhesives and the like.

  In particular, many studies have been made to use an aqueous urethane resin composition in the production of the industrial gloves. As a method for producing industrial gloves using the aqueous urethane resin composition, a method of coagulating the aqueous urethane resin composition in an aqueous solution containing a metal salt to produce a solidified film of the urethane resin is common. (For example, see Patent Document 1). However, this method requires a great amount of time and energy for the metal salt cleaning process, and environmental burden and cost increase of the final product are major issues.

JP-T-2006-524754

  The problem to be solved by the present invention is to provide a production method in which a water-based urethane resin composition can be solidified without using a metal salt, and a laminate having excellent texture can be obtained.

  In the present invention, the fiber base material is immersed in a coagulation bath (x) containing an alcohol solvent (i) having 2 to 6 carbon atoms and not containing a metal salt (ii), and then having an aromatic ring. Provided is a method for producing a coagulum, which is characterized by immersing in an aqueous urethane resin composition (y) containing an anionic urethane resin (A), a nonionic emulsifier (B), and an aqueous medium (C). Is.

  According to the production method of the present invention, since the solidification can be performed without using a metal salt, a metal salt washing step is unnecessary. Further, since an alcohol solvent having a relatively small number of carbon atoms is used as the coagulation bath, the load on the environment is small. Furthermore, the obtained laminate is excellent in texture. Therefore, the solidified product obtained by the production method of the present invention can be suitably used for production of gloves, paints, leather-like sheets and the like, and can be particularly suitably used for production of gloves.

  In the method for producing a coagulum according to the present invention, a fiber base material is immersed in a coagulation bath (x) containing an alcohol solvent (i) having 2 to 6 carbon atoms and not containing a metal salt (ii). Then, it is essential to immerse in an aqueous urethane resin composition (y) containing an anionic urethane resin (A) having an aromatic ring, a nonionic emulsifier (B), and an aqueous medium (C).

  As said fiber base material, a nonwoven fabric, a woven fabric, a knitting etc. can be used, for example. For example, polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, and blended fibers thereof are used as the fiber substrate. can do.

  In the present invention, it is essential that the coagulation bath (x) contains an alcohol solvent (i) having 2 to 6 carbon atoms. Since the alcohol solvent (i) is moderately strong in hydrophobicity, by using it in combination with the aqueous urethane resin composition (y) described later, a laminate having excellent coagulability and excellent texture can be obtained. It is done.

  Examples of the alcohol solvent (i) include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, and 2-methyl. -2-butanol, 1-hexanol, 2-hexanol, cyclohexanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol and the like can be used. These solvents may be used alone or in combination of two or more. Among these, since it has an isopropyl group having moderate hydrophobicity, it is preferable to use 2-propanol from the viewpoint of further improving the solidification property and the texture of the solidified product.

  Further, it is essential that the coagulation bath (x) does not contain the metal salt (ii). When the metal salt (ii) is contained, it is necessary to wash away the residue of the metal salt (ii) attached to the laminate having the solidified product. Examples of the metal salt (ii) include calcium nitrate, calcium chloride, and sodium chloride.

  Examples of the method of immersing the fiber base material in the coagulation bath (x) include a method of directly immersing the fiber base material in a tank storing the coagulation bath (x). The immersion time is, for example, in the range of 5 seconds to 10 minutes.

  Subsequently, this fiber base material is taken out and further immersed in the aqueous urethane resin composition (y), so that the aqueous urethane resin composition (y) is solidified, and on the surface of the fiber base material and in the vicinity of the surface. A laminate having a urethane solidified layer formed thereon is obtained.

  As a method of immersing the taken-out fiber substrate in the aqueous urethane resin composition (y), for example, the taken-out fiber substrate is directly placed in a tank in which the aqueous urethane resin composition (y) is stored. The method of immersing is mentioned. The immersion time is, for example, in the range of 5 seconds to 10 minutes. After this immersion, if necessary, it may be allowed to stand at room temperature for 1 to 30 minutes for the purpose of aging solidification.

  Moreover, after this immersion, for the purpose of drying the aqueous medium (C) in the aqueous urethane resin composition (y), for example, it may be dried at a temperature of 50 to 130 ° C. for 10 minutes to 2 hours.

  The aqueous urethane resin composition (y) used in the present invention must contain an anionic urethane resin (A) having an aromatic ring, a nonionic emulsifier (B), and an aqueous medium (C). . As the urethane resin, an anionic urethane resin having a low solvation among the water-based urethane resins is adopted, and an aromatic ring is further incorporated so that the resin is hardly dissolved in the alcohol solvent (i). Therefore, since it becomes difficult for a urethane resin to penetrate into the fiber base material, a laminate having an excellent texture can be obtained. Furthermore, by using an emulsifier having a nonionic group whose hydrophilicity is lowered by solvation in the alcohol solvent (i), excellent coagulation can be obtained without the metal salt (ii).

  Specifically, as the anionic urethane resin (A) having an aromatic ring, a polyol (a1) containing a polyol (a1-1) having a carboxyl group, an aromatic polyisocyanate (a2), and a chain extender ( It is preferable to use the reaction product of a3).

  The polyol (a1-1) having a carboxyl group imparts an anionic group to a urethane resin. For example, 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2, 2'-dimethylol butyric acid, 2,2'-valeric acid and the like can be used. These compounds may be used alone or in combination of two or more.

  The amount of the polyol (a1-1) used is preferably in the range of 0.05 to 10% by mass in the polyol (a1) from the viewpoint of obtaining more excellent solidification and texture. More preferably, it is in the range of 1 to 7% by mass.

  As the polyol (a1), as a polyol that can be used other than the polyol (a1-1), for example, polyether polyol, polyester polyol, polycarbonate polyol, dimer diol, acrylic polyol, polybutadiene polyol, and the like can be used. . These polyols may be used alone or in combination of two or more. These polyols can be appropriately determined according to the intended use.

  The number average molecular weight of the polyol is preferably in the range of 500 to 8,000, more preferably in the range of 800 to 5,000, from the viewpoint of durability. In addition, the number average molecular weight of the polyol indicates a value obtained by measurement under the following conditions by gel permeation column chromatography (GPC) method.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

  The aromatic polyisocyanate (a2) is preferably used from the point that a solidified film of urethane resin having a very good texture can be obtained. For example, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene poly Phenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, and the like can be used. These aromatic polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use diphenylmethane diisocyanate from the viewpoint that a more excellent texture can be obtained.

  The chain extender (a3) is an essential component in that a hard segment is formed in the urethane resin (A) to obtain practical durability as a solidified product, and the number average molecular weight is in the range of 50 to 450. Compounds can be used. As said chain extender (a3), the chain extender which has a hydroxyl group, the chain extender which has an amino group, etc. can be used, for example. These may be used alone or in combination of two or more.

  Examples of the chain extender having a hydroxyl group include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Aliphatic polyol compounds such as sucrose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc. Aromatic polyol compounds; water and the like can be used. These chain extenders may be used alone or in combination of two or more. Among these, it is preferable to use an aliphatic polyol compound from the viewpoint of easy availability of raw materials and easy discoloration.

  Examples of the chain extender having an amino group include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4. '-Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, etc. Can be used. These chain extenders may be used alone or in combination of two or more.

  The amount of the chain extender (a3) used is the sum of the polyol (a1), the aromatic polyisocyanate (a2), and the chain extender (a3) from the viewpoint that the durability of the solidified product can be further improved. The mass is preferably in the range of 0.5 to 20 mass%, more preferably in the range of 1 to 10 mass%.

  As a method for producing the anionic urethane resin (A), for example, a urethane prepolymer having an isocyanate group is produced by reacting the polyol (a1) with the aromatic polyisocyanate (a1). Method of producing by reacting the urethane prepolymer and the chain extender (a3); batch reaction of the polyol (a1), the aromatic polyisocyanate (a2) and the chain extender (a3) And the like. These reactions are preferably performed at a temperature of 50 to 100 ° C. for 3 to 10 hours, for example.

  The molar ratio of the total hydroxyl group and / or amino group of the polyol (a1) and the chain extender (a3) to the isocyanate group of the aromatic polyisocyanate (a2) [(isocyanate group) / (Total of hydroxyl group and amino group)] is preferably in the range of 0.8 to 1.2, more preferably in the range of 0.9 to 1.1.

  When producing the anionic urethane resin (A), it is preferable to deactivate the isocyanate group remaining in the anionic urethane resin (A). When the isocyanate group is deactivated, it is preferable to use an alcohol having one hydroxyl group such as methanol. As the usage-amount in the case of using the said alcohol, it is preferable that it is the range of 0.001-10 mass parts with respect to 100 mass parts of anionic urethane resins (A).

  Moreover, when manufacturing the said anionic urethane resin (A), you may use an organic solvent. Examples of the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetic ester compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; dimethylformamide and N-methylpyrrolidone. Amide compounds and the like can be used. These organic solvents may be used alone or in combination of two or more. The organic solvent is preferably removed by a distillation method or the like when obtaining an aqueous urethane resin composition.

  The content of the aromatic ring in the anionic urethane resin (A) obtained by the above method is in the range of 0.8 to 8 mol / kg from the viewpoint of further improving the coagulation property and the mechanical strength of the coagulum. It is preferable that the range is 1 to 6 mol / kg.

  The anionic urethane resin (A) preferably has a urea bond content of 1.2 mol / kg or less from the viewpoint that the discoloration over time can be controlled without impairing the texture.

  Since the urea bond is formed when the polyisocyanate reacts with a chain extender having an amino group or an amine formed by reacting isocyanate with water, the amount of the chain extender having an amino group used is reduced. The urea bond content of the anionic urethane resin (A) can be adjusted by adjusting and further urethanizing the isocyanate before emulsification. The urea bond content indicates a value calculated by the following general formula (1).

  Examples of the nonionic emulsifier (B) include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene. Nonionic emulsifiers having oxyethylene groups such as stearyl ether and polyoxyethylene sorbitol tetraoleate can be used, and the average added mole number of oxyethylene groups can further improve water dispersion stability and coagulation properties. From the viewpoint, the range is preferably 1 to 50, more preferably 3 to 30, and still more preferably 5 to 20. These nonionic emulsifiers may be used alone or in combination of two or more.

  As the usage-amount of the said nonionic emulsifier (B), it is 0.1-30 mass with respect to 100 mass parts of said anionic urethane resins (A) from the point which can further improve water dispersion stability and coagulability. The range of parts is preferable, and the range of 1 to 10 parts by mass is more preferable.

  As said aqueous medium (C), water, the organic solvent mixed with water, a mixture thereof, etc. can be used, for example. Examples of the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n- and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycol solvents such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl lactate solvents such as N-methyl-2-pyrrolidone and the like can be used. These aqueous media may be used alone or in combination of two or more. Among these, it is preferable to use only water or a mixture of water and an organic solvent miscible with water from the viewpoint of safety and reduction of environmental burden, and more preferably only water.

  The mass ratio [(A) / (C)] of the anionic urethane resin (A) and the aqueous medium (C) is in the range of 10/80 to 70/30 from the point that workability can be further improved. Is preferable, and the range of 20/80 to 60/40 is more preferable.

  The aqueous urethane resin composition (y) used in the present invention contains the anionic urethane resin (A), the nonionic emulsifier (B), and the aqueous medium (C) as essential components. And may contain a neutralizing agent, a crosslinking agent, and other additives.

  The neutralizing agent neutralizes the carboxyl group in the anionic urethane resin (A), for example, a non-volatile base such as sodium hydroxide or potassium hydroxide; trimethylamine, triethylamine, dimethylethanolamine, methyl Tertiary amine compounds such as diethanolamine and triethanol can be used. These neutralizing agents may be used alone or in combination of two or more.

  When using the neutralizing agent, it is added so as to have a molar ratio in the range of 0.8 to 1.2 with respect to the number of moles of carboxyl groups contained in the anionic urethane resin (A). It is preferable.

  The crosslinking agent is used to further improve mechanical strength by crosslinking with the anionic urethane resin (A). For example, a known melamine crosslinking agent, epoxy crosslinking agent, oxazoline crosslinking agent, carbodiimide crosslinking. An agent, an isocyanate crosslinking agent, or the like can be used.

  When using the said crosslinking agent, it is preferable that it is the range of 0.01-5 mass parts with respect to 100 mass parts of anionic urethane resins (A).

  Examples of the other additives include urethanization catalysts, silane coupling agents, thickeners, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light stabilizers, fluorescent whitening agents, foaming agents. Agent, pigment, dye, conductivity enhancer, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam, flame retardant, water absorbent, moisture absorbent, deodorant, foam stabilizer, antiblocking agent Agents, hydrolysis inhibitors and the like can be used. These additives may be used alone or in combination of two or more.

  As described above, according to the production method of the present invention, the metal salt can be solidified without using a metal salt, so that the metal salt washing step is unnecessary. Further, since an alcohol solvent having a relatively small number of carbon atoms is used as the coagulation bath, the load on the environment is small. Furthermore, the obtained laminate is excellent in texture. Therefore, the solidified product obtained by the production method of the present invention can be suitably used for production of gloves, paints, leather-like sheets and the like, and can be particularly suitably used for production of gloves.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Synthesis Example 1 Preparation of Aqueous Urethane Resin Composition (y-1) Polyether polyol (“PTMG2000” Mitsubishi Kasei Co., Ltd.) in the presence of 3,281 parts by weight of methyl ethyl ketone and 0.1 part by weight of stannous octylate Manufactured, number average molecular weight; 2,000) 1,000 parts by mass, 17 parts by mass of 2,2′-dimethylolpropionic acid, 47 parts by mass of ethylene glycol, and 344 parts by mass of diphenylmethane diisocyanate have a solution viscosity of 20, After reacting at 70 ° C. until reaching 000 mPa · s, 3 parts by mass of methanol was added to stop the reaction, and methyl ethyl ketone of an anionic urethane resin (A-1) having an aromatic ring content of 1.93 mol / kg A solution was obtained. The urethane resin solution is mixed with 70 parts by mass of polyoxyethylene distyrenated phenyl ether (HLB; 14) and 13 parts by mass of triethylamine, and then 800 parts by mass of ion-exchanged water is added to effect phase inversion emulsification. An emulsified liquid in which the water-soluble urethane resin (A-1) was dispersed in water was obtained.
Subsequently, methyl ethyl ketone was distilled off from the emulsion to obtain an aqueous urethane resin composition (y-1) having a nonvolatile content of 40% by mass.

[Synthesis Example 2] Preparation of aqueous urethane resin composition (y-2) Polyester polyol ("Placcel 220" manufactured by Daicel Corporation, in the presence of 3,281 parts by mass of methyl ethyl ketone and 0.1 part by mass of stannous octylate, Number average molecular weight; 2,000) 1,000 parts by mass, 17 parts by mass of 2,2′-dimethylolpropionic acid, 47 parts by mass of ethylene glycol, and 344 parts by mass of diphenylmethane diisocyanate have a solution viscosity of 20,000 mPa · s. After reacting at 70 ° C. until reaching s, 3 parts by mass of methanol was added to stop the reaction, and a methyl ethyl ketone solution of an anionic urethane resin (A-2) having an aromatic ring content of 1.93 mol / kg was obtained. Obtained. The urethane resin solution is mixed with 70 parts by mass of polyoxyethylene distyrenated phenyl ether (HLB; 14) and 13 parts by mass of triethylamine, and then 800 parts by mass of ion-exchanged water is added to effect phase inversion emulsification. An emulsified liquid in which the water-soluble urethane resin (A-2) was dispersed in water was obtained.
Subsequently, methyl ethyl ketone was distilled off from the emulsion to obtain an aqueous urethane resin composition (y-2) having a nonvolatile content of 40% by mass.

[Comparative Synthesis Example 1] Preparation of Aqueous Urethane Resin Composition (y′-1) Polyether polyol (“PTMG2000” Mitsubishi Kasei type) in the presence of 3,320 parts by mass of methyl ethyl ketone and 0.1 part by mass of stannous octylate Manufactured by Co., Ltd., number average molecular weight; 2,000) 1,000 parts by mass, 17 parts by mass of 2,2′-dimethylolpropionic acid, 47 parts by mass of ethylene glycol, and 407 parts by mass of dicyclohexylmethane diisocyanate Is reacted at 70 ° C. until it reaches 20,000 mPa · s, the reaction is stopped by adding 3 parts by mass of methanol, and an aliphatic anionic urethane resin (A ′ having an aromatic ring content of 0 mol / kg) A methyl ethyl ketone solution of -1) was obtained. After mixing 70 parts by mass of polyoxyethylene distyrenated phenyl ether (HLB; 14) and 13 parts by mass of triethylamine into this urethane resin solution, 800 parts by mass of ion-exchanged water is added to effect phase inversion emulsification. An emulsified liquid in which the group anionic urethane resin (A′-1) was dispersed in water was obtained.
Subsequently, methyl ethyl ketone was distilled off from the emulsion to obtain an aqueous urethane resin composition (y′-1) having a nonvolatile content of 40% by mass.

[Comparative Synthesis Example 2] Preparation of Aqueous Urethane Resin Composition (y′-2) Polyether polyol (“PTMG2000” Mitsubishi Kasei type) in the presence of 3,505 parts by mass of methyl ethyl ketone and 0.1 part by mass of stannous octylate Manufactured by Co., Ltd., number average molecular weight: 2,000) 1,000 parts by mass, 50 parts by mass of 2,2′-dimethylolpropionic acid, 47 parts by mass of ethylene glycol, and 407 parts by mass of diphenylmethane diisocyanate have a solution viscosity. After reacting at 70 ° C. until reaching 20,000 mPa · s, 3 parts by mass of methanol was added to stop the reaction, and an anionic urethane resin (A′-2) having an aromatic ring content of 1.93 mol / kg. ) Solution of methyl ethyl ketone. After mixing 38 parts by mass of triethylamine with this urethane resin solution, 800 parts by mass of ion-exchanged water was added to carry out phase inversion emulsification to obtain an emulsion in which the anionic urethane resin (A′-2) was dispersed in water. It was.
Subsequently, methyl ethyl ketone was distilled off from the emulsion to obtain an aqueous urethane resin composition (y′-2) having a nonvolatile content of 40% by mass.

[Example 1]
100 parts by mass of the aqueous urethane resin composition (X-1) obtained in Synthesis Example 1, 2 parts by mass of a thickener (“Borch Gel L75N” manufactured by Borcher), a carbodiimide crosslinking agent (“Carbodilite SV manufactured by Nisshinbo Chemical Co., Ltd.) −02 ”) 4 parts by mass and 200 parts by mass of ion-exchanged water were stirred for 2 minutes at 2,000 rpm with a mechanical mixer, and then defoamed with a vacuum deaerator to prepare a blended solution.
Next, a glove having a urethane coagulated layer on the fiber base material was prepared by the following procedure.

(1) A knitted glove made of nylon fiber is attached to the hand mold, dipped in a coagulation bath filled with 2-propanol for 10 seconds, and then pulled up.
(2) Next, the hand mold is dipped in the mixture solution for 10 seconds and pulled up.
(3) The hand mold is left at room temperature for 3 minutes to form a solidified film of urethane resin on the surface of the knitted glove.
(4) The hand mold is dried at 70 ° C. for 20 minutes and further at 120 ° C. for 30 minutes.
(5) Remove the knitted gloves from the hand mold.

[Example 2, Comparative Examples 1-2]
A glove was produced in the same manner as in Example 1 except that the type of the aqueous urethane resin composition used was changed as shown in the table.

[Comparative Example 3]
A glove was produced in the same manner as in Example 1 except that the coagulation bath used was changed from 2-propanol to a 2-propanol solution of calcium nitrate (concentration: 20%).

[Evaluation method of coagulation]
In Examples and Comparative Examples, when a urethane coagulated product layer could be formed, “◯” was evaluated, and when the urethane resin was dissolved during the coagulation bath immersion, “x” was evaluated.

[Texture evaluation method]
The gloves obtained in Examples and Comparative Examples were evaluated as follows according to the touch feeling when touched by hand.
“Good”: Excellent flexibility.
“×”; lack of flexibility.

Abbreviations in Table 1 will be described.
“MDI”; diphenylmethane diisocyanate “H ₁₂ MDI”: dicyclohexylmethane diisocyanate “(B-1)”: polyoxyethylene distyrenated phenyl ether (HLB; 14)
“IPA”; 2-propanol

  In Examples 1-2, it turned out that it can solidify without using a metal salt and the laminated body which is excellent in a texture is obtained.

  On the other hand, Comparative Example 1 was an embodiment using an aliphatic anionic urethane resin in place of the anionic urethane resin (A), but could not be solidified.

  Although the comparative example 2 is an aspect using the anionic urethane resin which does not contain a nonionic emulsifier (B), it was not able to coagulate | solidify.

  Comparative Example 3 is an embodiment in which a metal salt containing a metal salt is used as a coagulation bath, but the obtained glove has a poor texture, and the fiber base material is hard and brittle. There was also a problem that caused the torn.

Claims (3)

An anionic urethane resin having an aromatic ring is immersed in a coagulation bath (x) containing an alcohol solvent (i) having 2 to 6 carbon atoms and not containing a metal salt (ii). A method for producing a coagulum comprising immersing in an aqueous urethane resin composition (y) containing (A), a nonionic emulsifier (B), and an aqueous medium (C). The method for producing a coagulated product according to claim 1, wherein the anionic urethane resin (A) is made from an aromatic polyisocyanate (a2) as a raw material. The method for producing a coagulum according to claim 2, wherein the aromatic polyisocyanate (a2) is diphenylmethane diisocyanate.