JP2003201679A - Method for producing backing material for artificial leather with grain, and artificial leather with grain - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a backing material capable of obtaining an artificial leather with grains, excellent in feeling, peeling strength and bending resistance, a method for producing the backing material for an artificial leather with grains by using an aqueous polyurethane resin, and the artificial leather with grains obtained by performing a laminating process or coating process of a surface skin layer. <P>SOLUTION: This method for producing the backing material for the artificial leather with grains is characterized by impregnating a base substrate with a mixed liquid containing at least one kind selected from a group consisting of (A) an aqueous polyurethane liquid, (B) a urethane pre-polymer of which terminal isocyanate is blocked, in addition, (C) a polyamine compound and (D) a water soluble organic polymer, and then drying, and the artificial leather with grains is obtained by performing the laminating process or coating process of the surface skin layer on the backing material for the artificial leather with grains obtained by such method. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a flooring material for artificial leather with silver and an artificial leather with silver. More specifically, the present invention is obtained by a method for producing a floor material that gives an artificial leather with silver that is excellent in texture, peel strength and flex resistance, and by processing a skin layer on the floor material obtained by the production method. Regarding artificial leather with silver.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an artificial leather with silver, after a polyurethane resin skin layer formed by a dry method on a release paper is coated with an adhesive and dried,
Dry lamination method of bonding with a floor material impregnated with polyurethane resin, wet lamination method of bonding a floor material impregnated with polyurethane resin by coating an adhesive on the skin layer of polyurethane resin, and floor material impregnated with polyurethane resin It is known to use a dry coating process that coats a polyurethane resin that forms the skin layer on top and then dry it, or a wet coating process that coats the polyurethane resin that forms the skin layer on the floor material impregnated with the polyurethane resin and then performs water coagulation. ing.
Among these methods, a dry lamination method, a dry coating process, and a wet coating process are often used in view of the production stability of the artificial leather with silver and the quality such as texture. As the polyurethane resin used for these processes, solvent-based polyurethane resin, that is, N, N-, for impregnation of flooring, for skin layer, and for adhesives is used.
Polyurethane resins dissolved in organic solvents such as dimethylformamide, toluene and methyl ethyl ketone are often used. However, if a solvent-based polyurethane resin is used, it is possible to obtain a textured, peeling strength, and artificial leather with silver excellent in bending resistance, but there is concern about the environment of labor and work, and harmful solvents during processing. Since it is mixed with wastewater and exhaust and discharged, a great deal of labor and cost are required for the recovery process to prevent water pollution and air pollution. Therefore, as an alternative to solvent-based polyurethane resin, aqueous polyurethane resin for floor material impregnation and skin layer has been studied, but compared with silver-coated artificial leather using solvent-based polyurethane resin, texture and peeling At present, it is inferior in strength and bending resistance and has not been put into practical use. Also, as an adhesive for artificial leather with silver, which has excellent peel strength, a two-component water-based polyurethane adhesive composed of water-dispersed polyisocyanate and urethane polyol has been studied, but strong peeling of shoes, bags, etc. It is insufficient for products that require strength, and its use is currently limited.

[0003]

DISCLOSURE OF THE INVENTION The present invention is a flooring material from which an artificial leather with silver having excellent texture, peeling strength, and bending resistance can be obtained, and the artificial leather with silver uses an aqueous polyurethane resin. The purpose of the present invention is to provide a method for producing a flooring material for use, and a silver-coated artificial leather obtained by laminating or coating a skin layer on the flooring material obtained by the production method.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that in addition to a polyurethane aqueous solution and a urethane prepolymer-terminated isocyanate block, a polyamine compound or a water-soluble organic polymer is used. We have found that the artificial leather with silver produced by using the floor material obtained by impregnating the base material with a mixed solution containing molecules and then drying it has excellent texture, peel strength, and flex resistance. The present invention has been completed based on the above. That is, the present invention is at least selected from the group consisting of (C) polyamine compound and (D) water-soluble organic polymer in addition to (1) (A) polyurethane aqueous liquid and (B) urethane prepolymer-terminated isocyanate block product. A mixture containing one
A method for producing a flooring material for artificial leather with silver, which comprises impregnating a base material and then drying it. (2) (A) An isocyanate group obtained by reacting a polyisocyanate and a polyol with an aqueous polyurethane solution Terminal prepolymer, H
The method according to claim 1, which is obtained by emulsifying and dispersing in water using a nonionic surfactant of LB7 to 16 and then chain-extending with a polyamine compound having two or more amino groups and / or imino groups. A method of manufacturing a floor material for artificial leather with silver,
(3) (A) The aqueous polyurethane solution is a neutralized product of an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate, a polyol, and a compound having an anionic hydrophilic group and two or more active hydrogens with water. A method for producing a flooring material for artificial leather with silver according to claim 1, which is obtained by emulsifying and dispersing and then chain elongation reaction using a polyamine compound having two or more amino groups and / or imino groups.
(4) The method for producing a flooring material for artificial leather with silver according to item (1), wherein the (B) urethane prepolymer-terminated isocyanate block is a bisulfite-terminated isocyanate block, and (5) the (C) polyamine compound is A method for producing a flooring material for artificial leather with silver according to item 1, which is a compound having two or more amino groups and / or imino groups, (6) (D) the water-soluble organic polymer is methyl cellulose, ethyl cellulose, hydroxy A method for producing a flooring material for artificial leather with silver according to claim 1, which is at least one polymer selected from the group consisting of ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, sodium alginate, sodium polyacrylate and starch, and (7) A floor for artificial leather with silver obtained by the method according to any one of items 1 to 6. To, there is provided a grain-artificial leather, which is characterized by being obtained by laminating or coating process the skin layer. Furthermore, as a preferred embodiment of the present invention, (8) (A) an aqueous polyurethane liquid and (B)
The urethane prepolymer terminal isocyanate block product has a solid content weight ratio of (A) :( B) = 100: 500-
The method for producing a flooring material for artificial leather with silver according to claim 1, which is 100: 1, (9) (B) an isocyanate group regenerated from a urethane prepolymer-terminated isocyanate block product,
(C) The equivalent ratio of the polyamine compound to the total of amino groups, imino groups and nitrilo groups is 100: 300 to 100: 3.
The method for producing a flooring material for artificial leather with silver according to claim 1, which is 0,
And, (10) the weight of the resin derived from the (A) polyurethane aqueous liquid and (B) urethane prepolymer-terminated isocyanate block to be fixed to the base material is 3 to 200 parts by weight with respect to 100 parts by weight of the base material. There can be mentioned a method for producing a flooring material for artificial leather with silver according to item 1.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a flooring material for artificial leather with silver of the present invention, in addition to (A) polyurethane aqueous liquid and (B) urethane prepolymer-terminated isocyanate block, (C) polyamine compound and (D) A base material is impregnated with a mixed solution containing at least one selected from the group consisting of water-soluble organic polymers, and then dried. In the method of the present invention, the base material used for the production of the flooring material for artificial leather with silver may be a base material that is generally used for artificial leather without any particular limitation.
A knitted fabric and the like can be mentioned. Among these base materials,
Nonwoven fabrics using polyamide fibers, acrylic fibers, or polyester fibers can be preferably used because they provide a quality such as a texture close to that of natural leather. The thickness of the fibers forming the non-woven fabric is preferably 2.5 denier or less, more preferably 2 denier or less.
If the thickness of the fiber exceeds 2.5 denier, the texture of the artificial leather with silver becomes coarse and hard, and the quality is impaired, and the flex resistance may decrease. Also, the density of the non-woven fabric is 0.2
~ 0.7 g / cm ³ is preferred, 0.35-0.5
It is more preferably 5 g / cm ³ . If the density of the non-woven fabric is less than 0.2 g / cm ³ , the peel strength between the skin layer and the floor material for artificial leather with silver may decrease. When the density of the non-woven fabric exceeds 0.7 g / cm ³ , the texture of the artificial leather with silver becomes coarse and hard, the quality is impaired, and the bending resistance may be lowered.

In the method of the present invention, as the (A) polyurethane aqueous liquid, an aqueous liquid obtained by emulsifying and dispersing or solubilizing a polyurethane resin in water can be used. Among these, a forced emulsification type polyurethane aqueous solution which is emulsified and dispersed using an emulsifier and a self-emulsification type polyurethane aqueous solution which can be emulsified and dispersed without using an emulsifier can be preferably used. The forced emulsification type polyurethane aqueous solution is an isocyanate group-terminated prepolymer obtained by reacting (a) polyisocyanate and (b) polyol with HLB 7-16.
Is an aqueous liquid of a polyurethane resin obtained by emulsifying and dispersing in water using the nonionic surfactant of (1), and then performing a chain extension reaction with (c) a polyamine compound having two or more amino groups and / or imino groups. In the method of the present invention, H
LB is a value calculated by the Griffin formula. The self-emulsifying polyurethane aqueous liquid is an isocyanate group-terminated prepolymer obtained by reacting (a) polyisocyanate, (b) polyol and (d) a compound having an anionic hydrophilic group and two or more active hydrogens. Neutralized
This is an aqueous liquid of a polyurethane resin obtained by emulsifying and dispersing in water and then (c) chain elongation reaction using a polyamine compound having two or more amino groups and / or imino groups.

In the method of the present invention, as the polyisocyanate (a), aromatic polyisocyanates having two or more isocyanate groups, aliphatic polyisocyanates and alicyclic polyisocyanates can be used without particular limitation. , Aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3 Examples thereof include alicyclic polyisocyanates such as bis (isocyanatomethyl) cyclohexane. Among them, the aliphatic isocyanate or alicyclic polyisocyanate can be preferably used because the obtained (A) polyurethane aqueous solution becomes non-yellowing modified. Hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane Diisocyanate and 1,3-bis
(Isocyanatomethyl) cyclohexane can be used particularly preferably. The polyisocyanate (a) may be used alone or in combination of two or more.

In the method of the present invention, as the polyol (b), polyester polyol, polycarbonate polyol and polyether polyol having two or more hydroxyl groups can be preferably used. The average molecular weight of the polyol is preferably 500 to 4,000, more preferably 700 to 3,000. As the polyester polyol, for example, polyethylene adipate, polybutadiene adipate, polyethylene butylene adipate, polyhexamethylene isophthalate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, poly-ε-caprolactone diol, poly
(3-Methyl-1,5-pentylene) adipate, 1,6-
Polycondensate of hexanediol and dimer acid, 1,6-
Copolycondensates of hexanediol, adipic acid and dimer acid, polycondensates of nonanediol and dimer acid, polycondensates of ethylene glycol and dimer acid, copolycondensates of ethylene glycol, adipic acid and dimer acid, etc. be able to. As a polycarbonate polyol,
For example, polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly-1,4
-Cyclohexane dimethylene carbonate diol etc. can be mentioned. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide / propylene oxide, ethylene oxide / butylene oxide random copolymers and block copolymers. Further, a polyether polyester polyol having an ether bond and an ester bond may be used. These polyols can be used individually by 1 type, or can also be used in combination of 2 or more type.

In the method of the present invention, the compound (d) having an anionic hydrophilic group and two or more active hydrogens used for producing the self-emulsifying polyurethane aqueous solution is not particularly limited,
A compound in which the anionic hydrophilic group is a carboxyl group and the active hydrogen is hydrogen of a hydroxyl group can be preferably used. Examples of such compounds include 2,2
-Dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and the like can be mentioned. A polyester polyol having a pendant carboxyl group, which is obtained by reacting a dicarboxylic acid such as an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid with a diol having a carboxyl group can also be used. During the reaction, a diol having a carboxyl group may be mixed with a diol having no carboxyl group. These (d) compounds having an anionic hydrophilic group and two or more active hydrogens can be used alone or in combination of two or more. In the self-emulsifying polyurethane aqueous solution, the neutralized product of the isocyanate group-terminated prepolymer is the above-mentioned
Before or after synthesizing the isocyanate group-terminated prepolymer using the components (a), (b) and (d),
It is a neutralized product obtained by neutralizing the anionic hydrophilic group of the component (d). The compound used for neutralizing the anionic hydrophilic group is not particularly limited, and examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tributylamine,
Examples thereof include amines such as triethanolamine, sodium hydroxide, potassium hydroxide, and ammonia.

In a self-emulsifying polyurethane aqueous liquid,
The content of the anionic hydrophilic group derived from the component (d) is preferably 0.3 to 4.5% by weight, and more preferably 0.5 to 2.0% by weight based on the weight of the polyurethane resin. More preferable. If the content of the anionic hydrophilic group is less than 0.3% by weight, emulsification may be difficult or the emulsion stability may be insufficient. When the content of the anionic hydrophilic group exceeds 4.5% by weight, the water resistance of the polyurethane resin may decrease. Using each of the above components,
When synthesizing an isocyanate group-terminated prepolymer, that is, a urethane prepolymer having an isocyanate group at the terminal, a chain extender (e) can be used if necessary. Examples of the chain extender (e) include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol and sorbitol. The chain extender may be used alone or in combination of two or more. The method for producing the isocyanate group-terminated prepolymer is not particularly limited, and for example, it can be produced by a conventionally known one-step so-called one-shot method, a multi-step isocyanate polyaddition reaction method, or the like. The reaction temperature is
It is preferably 40 to 150 ° C.

In the method of the present invention, when the isocyanate group-terminated prepolymer of the forced emulsion type aqueous polyurethane solution is emulsified and dispersed in water, it is preferable to use a nonionic surfactant of HLB 7 to 16 and a nonionic surfactant of HLB 9 to 15. It is more preferable to use an ionic surfactant. When the HLB is less than 7, it becomes difficult to emulsify and disperse the prepolymer, and the stability may be poor even when the prepolymer is dispersible. H
When LB exceeds 16, it becomes difficult to emulsify and disperse the prepolymer, and even when the prepolymer can be dispersed, the resulting polyurethane resin may have poor water resistance. The structure of the nonionic surfactant used is not particularly limited, and examples thereof include polyoxyethylene distyryl phenyl ether type nonionic surfactants, polyoxyethylene propylene distyryl phenyl ether type nonionic surfactants, and polyoxyethylene trioxide. Examples thereof include styryl phenyl ether type nonionic surfactants, polyoxyethylene propylene tristyryl phenyl ether type nonionic surfactants and pluronic type nonionic surfactants. These nonionic surfactants can be used alone or in combination of two or more. The amount of these nonionic surfactants used can be appropriately selected depending on the hydrophilicity derived from the polyoxyethylene group of the isocyanate group-terminated prepolymer, which is the substance to be emulsified, but is usually the isocyanate group-terminated prepolymer. 1
The amount is preferably 0.5 to 10 parts by weight, more preferably 1 to 6 parts by weight, based on 00 parts by weight. When the amount of the nonionic surfactant used is less than 0.5 part by weight based on 100 parts by weight of the isocyanate group-terminated prepolymer, it may be difficult to obtain a stable emulsion-dispersed state. When the amount of the nonionic surfactant used exceeds 10 parts by weight with respect to 100 parts by weight of the isocyanate group-terminated prepolymer, the water resistance of the resulting polyurethane resin may decrease. In the self-emulsifying polyurethane aqueous solution, the neutralized product of the isocyanate group-terminated prepolymer is
Although it can be emulsified and dispersed in water without adding an emulsifier, a nonionic surfactant of HLB 7 to 16 can be used if necessary.

In the method of the present invention, mechanical shearing force is preferably used because phase inversion emulsification occurs when the isocyanate group-terminated prepolymer or the neutralized product of the isocyanate group-terminated prepolymer is emulsified and dispersed in water. There is no particular limitation on the emulsifying device that gives a mechanical shearing force, and examples thereof include a homomixer and a homogenizer. The isocyanate group-terminated prepolymer or the neutralized product of the isocyanate group-terminated prepolymer may be at room temperature to 40 ° C.
It is preferable to suppress the reaction between the isocyanate group and water or the nonionic surfactant as much as possible by emulsifying and dispersing in water in the temperature range of. Furthermore, if necessary, phosphoric acid,
A reaction inhibitor such as sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluene sulfonic acid, adipic acid, benzoyl chloride can be added. In the method of the present invention, after the isocyanate group-terminated prepolymer or a neutralized product of the isocyanate group-terminated prepolymer is emulsified and dispersed in water, (c) a polyamine compound having two or more amino groups and / or imino groups is used. A chain extension reaction is performed to obtain an aqueous polyurethane solution. Examples of the compound (c) having two or more amino groups and / or imino groups include ethylenediamine, tetramethylenediamine, hexamethylenediamine, hydrazine, piperazine, isophoronediamine, norbornanediamine, diaminodiphenylmethane, tolylenediamine and xylylenediamine. Examples thereof include diamines such as amines, polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and iminobispropylamine. Among these, ethylenediamine, hydrazine, piperazine, isophoronediamine, norbornanediamine, diethylenetriamine and iminobispropylamine can be preferably used. These polyamine compounds are
One kind may be used alone, or two or more kinds may be used in combination. The chain extension reaction of an isocyanate group-terminated prepolymer or a neutralized product of an isocyanate group-terminated prepolymer can be carried out by adding (c) a polyamine compound to an emulsion dispersion of these prepolymers, or (c) a polyamine It is also possible to add an emulsified dispersion of a prepolymer to the compound. The chain extension reaction is preferably carried out at a reaction temperature of 20 to 40 ° C., and usually completed in 30 to 120 minutes.

The (B) urethane prepolymer terminal isocyanate blocked product used in the method of the present invention is a urethane prepolymer having hydrophilicity and heat reactivity, and is a compound in which the terminal isocyanate group is blocked by a blocking agent. . The urethane prepolymer-terminated isocyanate blocked product can be stored for a long time in the state of an aqueous solution, the blocking agent is desorbed by heating, the active isocyanate group is regenerated, and the polyaddition reaction in the urethane prepolymer molecule or between molecules is performed. To give a polyurethane polymer, or to undergo an addition reaction with other functional groups. The desorption temperature of the blocking agent is 50 to 150 ° C.
Is preferred. The urethane prepolymer-terminated isocyanate blocked product is (f) a compound having two or more active hydrogens, (g) a polyisocyanate compound having two or more isocyanate groups, and optionally (h) 2.
It can be produced by blocking the terminal isocyanate group of the urethane prepolymer obtained by reacting a chain extender having one or more active hydrogens with a blocking agent.

Examples of the compound (f) having two or more active hydrogens include compounds having two or more hydroxyl groups, carboxyl groups, amino groups, mercapto groups, etc. at the end or in the molecule, Polyether, polyester, polyether ester, polycarbonate and the like can be preferably used. As the polyether, for example, ethylene oxide, propylene oxide, styrene oxide, homopolymers such as epichlorohydrin, random or block copolymers, or,
Examples thereof include addition polymers to polyhydric alcohols. As polyester and polyether ester,
For example, polyvalent saturated carboxylic acids such as adipic acid, succinic acid, phthalic acid and maleic anhydride, unsaturated carboxylic acids or their acid anhydrides, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol Mainly obtained from polyvalent saturated alcohols such as 1,6-hexanediol and trimethylolpropane, unsaturated alcohols, polyalkylene ether glycols such as polyethylene glycol and polypropylene glycol having a relatively low molecular weight, or a mixture thereof. Examples thereof include linear or branched condensation products, polyesters obtained from lactones or hydroxy acids, and polyether esters obtained by adding ethylene oxind, propylene oxide and the like to previously produced polyesters.

As the polyisocyanate (g), aromatic polyisocyanates having two or more isocyanate groups, aliphatic polyisocyanates and alicyclic polyisocyanates can be used without particular limitation. Xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, aromatic polyisocyanates such as naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,
Examples thereof include alicyclic polyisocyanates such as 3-bis (isocyanatomethyl) cyclohexane. Among them, the aliphatic isocyanate or alicyclic polyisocyanate can be preferably used because the obtained (B) urethane prepolymer terminal isocyanate block product is non-yellowing modified, hexamethylene diisocyanate,
Isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane can be particularly preferably used. The polyisocyanate (g) may be used alone or in combination of two or more. (h) Examples of chain extenders having two or more active hydrogens include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, glycerin, trimethylolpropane, and pentaerythritol. And the like, diamines such as ethylenediamine, hexamethylenediamine, piperazine, aminoalcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethyleneglycol, and water.

(F) a compound having two or more active hydrogens,
(g) A polyisocyanate compound having two or more isocyanate groups, and (h) a method of reacting a chain extender having two or more active hydrogens to produce a urethane prepolymer is not particularly limited. Instead, for example, it can be produced by a conventionally known one-step so-called one-shot method, a multi-step isocyanate polyaddition reaction method, or the like.
The reaction conditions are not particularly limited, but the reaction temperature is preferably 150 ° C or lower, more preferably 50 to 120 ° C. The reaction time is usually 5 minutes to several hours.
Further, the molar ratio of isocyanate group / active hydrogen is 1 or more, but since a blocked isocyanate structure having heat reactivity is required, it is essential that free isocyanate groups remain in the resulting urethane prepolymer. Is. The content of the free isocyanate group is preferably 1 to 10% by weight, more preferably 2 to 7% by weight. If the content of free isocyanate groups is less than 1% by weight or more than 10% by weight, the water-solubility of the urethane prepolymer-terminated isocyanate block obtained becomes unstable, causing separation and gelation over time. May occur.

Examples of the blocking agent for the urethane prepolymer-terminated isocyanate block used in the method of the present invention include:
There is no particular limitation as long as it reacts with a terminal isocyanate group, is hydrophilic, and can be easily desorbed under the conditions of a thermal reaction to regenerate an active isocyanate group, and examples thereof include bisulfite, oxime, and alcohol. Can be mentioned. Of these, bisulfite can be used particularly preferably because it has a low desorption temperature. The reaction between the urethane prepolymer and the aqueous solution of bisulfite is an exothermic reaction, which is a competitive reaction between bisulfite and water.Therefore, in order to selectively block the bisulfite selectively, the reaction temperature Is 5
It is preferably 0 ° C. or lower, more preferably 20 to 40 ° C. The reaction time is preferably 5 minutes to 2 hours. After the completion of the reaction, the product is diluted with water to an appropriate concentration to obtain a hydrophilic and heat-reactive urethane prepolymer-terminated isocyanate block product. This block can be stored for a long time in the state of an aqueous solution, and by heating at 50 to 150 ° C., the bisulfite of the blocking agent dissociates to regenerate an active isocyanate group, so that the prepolymer molecule or A polymerization addition reaction occurs between molecules to give a polyurethane polymer, or addition to other functional groups occurs.

The polyamine compound (C) used in the method of the present invention is preferably a compound having two or more amino groups, imino groups and / or nitrilo groups. By using this (C) polyamine compound, an artificial leather with silver having a soft texture can be obtained. (C) Polyamine compounds include, for example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, hydrazine, piperazine, isophoronediamine, norbornanediamine, diaminodiphenylmethane, tolylenediamine, xylylenediamine, triethylenediamine, diethylenetriamine, triethylenetetramine, Examples thereof include tetraethylenepentamine, iminobispropylamine, tetramethylhexamethylenediamine and the like. Among these, compounds having two or more amino groups and / or imino groups are particularly preferable, and ethylenediamine, hydrazine, piperazine, isophoronediamine, norbornanediamine, diethylenetriamine and iminobispropylamine are particularly preferably used. it can.

Examples of the water-soluble organic polymer (D) used in the method of the present invention include gums such as guar gum, psyllium gum, gum arabic, tragacanth gum, karaya gum, locust bean gum, tara gum, tamarind gum and alapinogalactan. Pectin, agar, carrageenan, ferceran, alginic acid or a salt thereof, proteins such as wheat protein, soy protein, corn protein, potato protein, microcrystalline cellulose, corn hemicellulose,
Water-soluble organic polymers obtained from plants such as mannan,
Water-soluble organic polymers obtained from microorganisms such as xanthan gum, duran gum, curdlan, dextran, levan, cyclodextrin, pullulan, water-soluble organic polymers obtained from animal bodies such as glue, gelatin, casein, milk protein, albumin, collagen Polymer, alkyl cellulose, hydroxyl alkyl cellulose, alkyl hydroxy alkyl cellulose, carboxy alkyl cellulose, carboxy hydroxy alkyl cellulose, sulfated cellulose, cellulose phosphate, carboxymethyl starch, dialdehyde starch, starch hydrogenation product, polydextrose, polyvinyl pyrrolidone ,
Semi-synthetic and synthetic water-soluble organic polymers such as polyvinyl alkyl ether, polyacrylic acid, polymethacrylic acid and salts thereof, polyacrylamide, propylene glycol ether alginate and the like can be mentioned. Among these, methyl cellulose, ethyl cellulose, hydroxyl ethyl cellulose, hydroxyl propyl cellulose, carboxymethyl cellulose, sodium alginate, sodium polyacrylic acid salt and starch can be preferably used, and hydroxyl ethyl cellulose, carboxymethyl cellulose and sodium alginate are particularly preferably used. be able to. By using the water-soluble organic polymer (D), it is possible to enhance the water absorption retention and accelerate the gelation of the (A) polyurethane aqueous solution.

In the method of the present invention, the (A) aqueous polyurethane solution and the (B) urethane prepolymer-terminated isocyanate block product have a weight ratio in terms of solid content of (A) :( B).
= 100: 500 to 100: 1 is preferable.
If the weight ratio in terms of solid content is less than (A) :( B) = 100: 500, there are many active isocyanate groups that are regenerated after deblocking of the urethane prepolymer-terminated isocyanate block of (B), and they are fixed to the substrate. The cross-linking density of the resin is increased, the texture of the floor material for artificial leather with silver becomes coarse and hard, the texture of the resulting artificial leather with silver becomes coarse and hard, and the flex resistance may be further reduced. The weight ratio in terms of solid content is
When (A) :( B) = 100: 1 is exceeded, there are few active isocyanate groups regenerated after deblocking of the urethane prepolymer-terminated isocyanate block of (B), and the cross-linking density of the resin adhered to the substrate becomes low. As a result, the strength of the floor material for artificial leather with silver becomes low, and the peel strength between the floor material and the skin layer may decrease. In the method of the present invention, the strength of the floor material for artificial leather with silver can be improved by using the (A) polyurethane aqueous solution and (B) urethane prepolymer-terminated isocyanate block.

In the method of the present invention, the equivalent ratio of (B) the isocyanate group regenerated from the urethane prepolymer-terminated isocyanate block product to (C) the total of amino groups, imino groups and nitrilo groups of the polyamine compound is 100: 3.
It is preferably from 00 to 100: 30. If the equivalent ratio of the isocyanate group to the total of amino group, imino group and nitrilo group is less than 100: 300, the crosslink density of the fixing resin becomes high and the texture of the flooring material becomes coarse and hard, so that the obtained silver is obtained. The texture of the artificial leather with a rough surface becomes coarse and hard, and the bending resistance may be reduced. When the equivalent ratio of the isocyanate group to the total of amino group, imino group, and nitrilo group exceeds 100: 30, the crosslink density of the fixing resin becomes low and the strength of the floor material becomes low. Peel strength may decrease. The (C) polyamine compound reacts with the isocyanate groups regenerated by deblocking the urethane prepolymer-terminated isocyanate block of (B) to form strong crosslinks and improve the strength of the flooring material. In the method of the present invention, the weight ratio of (A) polyurethane aqueous liquid to (D) water-soluble organic polymer in terms of solid content is (A) :( D) = 100: 1.
It is preferably from 00 to 100: 2.5. If the weight ratio in terms of solid content is less than (A) :( D) = 100: 100, the viscosity of the mixed solution used for producing the flooring material increases,
It may be difficult to perform stable impregnation. When the weight ratio in terms of solid content exceeds (A) :( D) = 100: 2.5, the uniformity of the resin adhered to the substrate becomes insufficient and the strength becomes weak, and the floor material and the skin layer There is a risk that the peel strength with (D) By using a water-soluble organic polymer, (A) polyurethane aqueous liquid migration that occurs during drying is prevented, the homogeneity of the resin adhered to the substrate is increased, and stable strength is obtained, and silver It is possible to improve the bending resistance of the artificial leather provided with.

In the method of the present invention, in addition to (A) the aqueous polyurethane solution and (B) the urethane prepolymer-terminated isocyanate block, (C) a polyamine compound and (D)
At least one selected from the group consisting of water-soluble organic polymers
A base material such as a non-woven fabric, a woven fabric, and a knitted fabric is impregnated with a mixed solution containing seeds, and then dried to obtain a flooring material for artificial leather with silver. In the method of the present invention, there is no particular limitation on the method of impregnating the substrate with the above mixed solution, for example, a dipping method,
A pad method, a spray method, a spray method or the like can be applied. Among these, the dipping method and the pad method can be preferably used. The concentration of the mixed solution and the treatment conditions can be appropriately selected, but the weight of the resin derived from the (A) polyurethane aqueous solution and (B) the urethane prepolymer-terminated isocyanate block product fixed to the substrate is 100% by weight of the substrate. It is preferably 1 to 300 parts by weight, more preferably 3 to 200 parts by weight, and 5 to 100 parts by weight.
More preferably, it is 150 parts by weight. When the amount of resin adhered is less than 3 parts by weight with respect to 100 parts by weight of the base material,
The resulting flooring material may have low strength, and the peeling strength between the flooring material and the skin layer may decrease. If the amount of resin adhered exceeds 200 parts by weight with respect to 100 parts by weight of the base material, the texture of the flooring material becomes rough and the texture of the obtained artificial leather with silver becomes coarse and hard, and the bending resistance may decrease. There is.

In the method of the present invention, the resin is adhered to the substrate by impregnating the above-mentioned mixed solution and then drying. There is no particular limitation on the drying method, and for example, dry heat drying using a pin tenter or the like, high ten pulper steamer (HTS), high pressure steamer (H.S.
Wet heat drying using P.S.), far infrared ray drying, microwave drying and the like. Among them, the wet heat drying using a high temperature pulper steamer, a high pressure steamer or the like can be preferably used because the obtained flooring material has a good texture and the processing cost is low. In the method of the present invention, in order to improve the texture of the artificial leather with silver, in the above mixed solution, a polyamide resin,
Synthetic resin dispersion such as polyimide resin, polyamino resin, polyacrylic resin, polyvinyl acetate resin, ethylene / vinyl acetate resin, polyvinyl chloride resin, epoxy resin, polyester resin, and NB
Latex dispersions such as R, SBR, EPR, polybutadiene rubber, butyl rubber and natural rubber can be mixed. In the method of the present invention, the floor material for artificial leather with silver can be colored, if necessary. The coloring method is not particularly limited, and examples thereof include a coloring method such as a method of impregnating a pigment in a mixed solution, a post-dyeing method of dyeing after impregnation, and a pre-dyeing method of dyeing before impregnation. It is preferable to use an aqueous pigment as the pigment from the viewpoint of the fastness of the obtained floor material for artificial leather with silver and the processing cost.

The silver-coated artificial leather of the present invention can be obtained by laminating or coating the skin layer on the silver-coated artificial leather floor material produced by the method of the present invention. There is no particular limitation on the material of the skin layer, for example, polyurethane resin, polyamide resin, polyimide resin,
Synthetic resins such as polyamino resins, polyacrylic resins, polyvinyl acetate resins, ethylene / vinyl acetate resins, polyvinyl chloride resins, epoxy resins, polyester resins, NBR, SBR, EPR, polybutadiene rubber, It can be formed using a latex such as butyl rubber or natural rubber. Of these, polyurethane resins are preferred because the resulting artificial leather with silver has a soft texture. There is no particular limitation on the method for forming the skin layer, and an aqueous resin using water as a solvent, or a solvent-based resin using a solvent as a solvent can be used, but in view of working environment and environmental problems, an aqueous resin is used. Is preferably used. As the aqueous polyurethane resin, a polyurethane aqueous solution similar to the forced emulsification type or self-emulsification type polyurethane aqueous solution used as the (A) polyurethane aqueous solution can be used. Among them, the self-emulsifying polyurethane aqueous solution can be preferably used because the film-forming property and strength of the skin layer are improved. In order to improve the heat resistance and water resistance of the skin layer,
It is preferable to use these resins in combination with a crosslinking agent such as carbodiimide, oxazoline and epoxy. Further, various surfactants such as fluorine type and acetylene glycol type can be added as a leveling agent, and N-methylpyrrolidone, propylene glycol monomethyl ether acetate and the like can be added as a solvent. Furthermore, if necessary, a filler, a softening agent, an antiaging agent, a stabilizer, an adhesion promoter, an antifoaming agent, a coloring agent such as a pigment, and the like can be used in combination.

In the present invention, either a dry lamination method or a wet lamination method can be applied as a method for laminating the skin layer on the artificial leather floor material with silver. Among them, the dry lamination method can be preferably used because the obtained artificial leather with silver has a good texture. In the dry lamination method, using a thickener, the viscosity is 1,000 to 15,000 mP.
The resin preparation for the skin layer adjusted to a · s is coated on the release paper so that the coating film thickness is 0.1 to 200 μm, and dried in a dryer at 40 to 180 ° C. to form the skin layer. Let it form. Then, an adhesive whose viscosity was adjusted to 1,000 to 15,000 mPa · s using a thickener was coated on the skin layer so that the coating film thickness was 0.1 to 200 μm, and the thickness was 40 to 180. Dry in a dryer at ℃. Further, this adhesive layer and the flooring material for artificial leather with silver obtained by the method of the present invention are attached to each other at a temperature of 20 to 1
Laminate with a nip roll at 30 ° C. and a pressure of 0.98 to 29.4 MPa. After lamination, it is preferable to age to stabilize the peel strength between the skin layer and the floor material, and more preferably to age at a temperature of 30 to 70 ° C for 1 to 3 days. After completion of aging, the release paper is peeled off to obtain artificial leather with silver.

The adhesive used for laminating is not particularly limited, and for example, an acrylic adhesive, a polyurethane adhesive, a vinyl acetate adhesive or the like can be used. The form of the adhesive is preferably an aqueous resin using water as a solvent from the viewpoint of working environment and environmental problems, but a solvent-based resin using a solvent as a solvent may be used if necessary. Among these adhesives, polyurethane adhesives are preferable from the viewpoint of the texture of the artificial leather with silver. Examples of the water-based polyurethane adhesive include a one-component polyurethane adhesive and a two-component polyurethane adhesive composed of a water-dispersible polyisocyanate curing agent and a water-based polyurethane main agent. In these adhesives, if necessary, various surfactants such as fluorine-based and acetylene glycol-based leveling agents,
As a solvent, N-methylpyrrolidone, propylene glycol monomethyl ether acetate or the like can be added. Further, if necessary, a filler, a softening agent, an antiaging agent, a stabilizer, an adhesion promoter, an antifoaming agent, a colorant such as a pigment and the like can be added. As the thickener for the skin layer and the adhesive, any thickener that does not interfere with the performance such as film-forming property and adhesiveness can be used without particular limitation.

The method for coating the resin preparation for the skin layer and the adhesive is not particularly limited, and examples thereof include roll coating, gravure coating, knife coating, reverse coating and kiss coating. The dryer is not particularly limited, and examples thereof include a hot air dryer, an infrared irradiation dryer, a microwave irradiation dryer and a wet heat dryer. In the present invention, as a method for coating the surface layer of the artificial leather flooring with silver, either a dry coating process or a wet coating process can be applied, but in view of the processing cost, the dry coating process is used. It can be preferably used. In the dry coating process, a resin preparation for the skin layer, whose viscosity is adjusted to 1,000 to 15,000 mPa · s using a thickener, is applied to the floor material for artificial leather with silver and the coating film thickness is 0. After coating so as to have a thickness of 1 to 200 μm, it is dried in a dryer at 40 to 180 ° C. to obtain artificial leather with silver. The coating method is not particularly limited, and examples thereof include roll coating, gravure coating, knife coating, reverse coating, and kiss coating. The dryer is also not particularly limited, and examples thereof include a hot air dryer, an infrared irradiation dryer, a microwave irradiation dryer, and a wet heat dryer.

[0028]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The performance of the artificial leather with silver obtained in Examples and Comparative Examples was evaluated by the following method. (1) Peel strength test The artificial leather with silver is cut into a size with a width of 25 mm and a length of 150 mm, and a kraft tape is attached to the skin layer side using an iron at a temperature of 110 ° C. Tensile tester [Shimadzu Corporation, AU
TOGRAPH AG-500D], pulling speed 200mm
/ Min, peel strength is measured by T-type peel test. In addition, in the process of measuring the peel strength, when the floor material for artificial leather with silver is broken, it is referred to as "floor material destruction", and when the adhesive interface is destroyed, it is referred to as "adhesive interface failure". (2) The texture of the artificial leather with silver is evaluated in terms of texture in 5 grades from 1st grade (coarse hard) to 5th grade (soft). (3) Flex resistance test The flex resistance of artificial leather with silver was measured according to JIS K 6545-19.
Measure according to 94. A bending tester [No. 197 FLEXOMETER, Yasuda Seiki Seisakusho Co., Ltd.] was used as a testing machine, and the state of damage on the test piece after bending 200,000 times was visually inspected as Class 1 (cut or marked crack). ) To 5th grade (no cracks occur).

Further, in the examples and comparative examples, the following agents were used. (1) Polyurethane aqueous liquid for the skin layer of drug used in Examples and Comparative Examples Implaner DLV [Bayer Co., Ltd., solid content 40% by weight] Implaner DLF [Bayer Co., Ltd., solid content 40% by weight] Adhesion Agent component Neocello 10A [Nichika Chemical Co., Ltd., 1-pack type water-based polyurethane adhesive] Evaphanol HO-10 [Nikaka Chemical Co., Ltd., water-based polyurethane, main component of 2-pack adhesive] BAIHIJUR 3100 [Sumitomo Bayer Urethane] (stock),
Water-dispersed polyisocyanate, curing agent for two-component adhesives] NEO Sticker N [Nikaka Chemical Co., Ltd., thickener] (2) Chemicals used only in Comparative Examples Solvents for floor materials for artificial leather with silver -Based polyurethane resin Evaphanol ALS-30 [Nikaka Chemical Co., Ltd., polyurethane resin, solid content 30% by weight] NK Assist F-100, a film forming aid for artificial leather flooring materials [Nikaka Chemical Co., Ltd., Solid content 100
% By weight] NK Assist F-200 [Nichika Chemical Co., Ltd., solid content 100
% By weight] Peaklon 700 [Nikaka Chemical Co., Ltd., solid content 100% by weight] Solvent-based polyurethane resin Evaphanol D-5080 [Nikaka Chemical Co., Ltd., solid content 3 for skin layer]
0% by weight] Two-component solvent-based adhesive Neocello 150 [Nikaka Chemical Co., Ltd., solvent-based polyurethane resin, main agent] Coronate L [Japan Polyurethanes Co., Ltd., solvent-based isocyanate, curing agent] The solid content is , 5g sample in a petri dish, 105 ℃
The heating residue (% by weight) after standing for 3 hours in a dryer (Perfect Oven PV-210, Tabai Espec Co., Ltd.).

Production Example 1 (Production of Polyurethane Aqueous Liquid) Polytetramethylene glycol (average molecular weight 1,000) 76.1 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube. Parts by weight, polyoxyethylene oxypropylene random copolymer glycol (average molecular weight 1,000, oxyethylene group content 70% by weight)
16.9 parts by weight, 1,4-butanediol 1.5 parts by weight,
Trimethylolpropane 1.9 parts by weight, dibutyltin dilaurate 0.001 parts by weight and methyl ethyl ketone 60
After adding 4 parts by weight of dicyclohexylmethane diisocyanate to the mixture,
The reaction was carried out at 300 ° C. for 300 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 2.1% by weight based on the solid content. After cooling this solution to 30 ° C. or lower, 0.1 part by weight of decyl phosphate and 6.0 parts by weight of polyoxyethylene tristyryl phenyl ether (HLB = 15) were added and mixed uniformly, and then added to another container. And use a disper blade to add water 2
54 parts by weight were gradually added to perform phase inversion emulsification and dispersion, and a polyamine solution prepared by dissolving 2.0 parts by weight of piperazine and 0.8 parts by weight of diethylenetriamine in 11.3 parts by weight of water was added thereto and stirred for 90 minutes. A polyurethane dispersion was obtained. The obtained polyurethane dispersion was further subjected to solvent removal under reduced pressure at 50 ° C. to obtain a solid content of 35.2% by weight and a viscosity of 45 mPa · s (BM viscometer, No. 1 rotor, 30 rp).
m.), and a stable polyurethane aqueous solution having an average particle diameter of 0.34 μm was obtained. This polyurethane aqueous solution is referred to as polyurethane aqueous solution A1. Production Example 2 (Production of Aqueous Polyurethane Liquid) Polytetramethylene glycol (average molecular weight 1,000) 60.0 parts by weight and 1.4
1.4 parts by weight of butanediol, 6.6 parts by weight of 2,2-dimethylolbutanoic acid, 1.0 part by weight of trimethylolpropane, 0.005 part by weight of dibutyltin dilaurate and 67.0 parts by weight of methyl ethyl ketone, After mixing uniformly, dicyclohexylmethane diisocyanate 4
Add 0.0 parts by weight and react at 85 ° C for 250 minutes to obtain a free isocyanate group content of 2.6% by weight based on the solid content.
A methyl ethyl ketone solution of the urethane prepolymer was obtained. The solution is cooled to 30 ° C. and triethylamine 2.
After 5 parts by weight was added to neutralize, 180.0 parts by weight of water was gradually added to emulsify and disperse. A polyamine solution prepared by dissolving 2.7 parts by weight of piperazine in 20.0 parts by weight of water was added to this emulsified dispersion, and the mixture was stirred for 90 minutes to obtain a polyurethane dispersion. The resulting polyurethane dispersion was subjected to solvent removal under reduced pressure at 50 ° C. to give a solid content of 35.
A stable polyurethane aqueous solution having a weight percentage of 5%, a viscosity of 60 mPa · s (BM viscometer, No. 1 rotor, 30 rpm) and an average particle diameter of 0.12 μm was obtained. This polyurethane aqueous solution is referred to as polyurethane aqueous solution A2. Production Example 3 (Production of urethane prepolymer-terminated isocyanate block product) Polyoxyethylene oxypropylene random copolymer glycol (average molecular weight 2,200, oxyethylene group content 50% by weight) 13 was placed in the same reactor as in Production Example 1.
2.7 parts by weight and 27.1 parts by weight of a propylene oxide adduct of glycerin (average molecular weight 1,500) were charged and uniformly mixed, and then isophorone diisocyanate 40.
2 parts by weight was added, and the mixture was reacted at 120 ° C. for 360 minutes to obtain a urethane prepolymer having a free isocyanate group content of 4.0% by weight. This urethane prepolymer was cooled to 30 ° C., 85.0 parts by weight of isopropyl alcohol was added and uniformly mixed, and 35.5 parts of anhydrous sodium bisulfite was previously prepared.
An aqueous solution obtained by dissolving 6 parts by weight of water in 66.7 parts by weight of water was gradually added, and a blocking reaction with bisulfite was performed at 30 ° C. for 60 minutes. 600 parts by weight of water was added to the reaction solution to obtain a urethane prepolymer-terminated isocyanate block dispersion. The resulting urethane prepolymer-terminated isocyanate block dispersion has a solid content of 30.0% by weight and a viscosity of 40 m.
It was a stable dispersion of Pa.s (BM viscometer, No. 1 rotor, 30 rpm). This urethane prepolymer terminal isocyanate block dispersion is referred to as terminal isocyanate block dispersion B.

Preparation Example 1 (Surface layer film for laminating) A polyurethane preparation for the skin layer having the composition shown below and having a viscosity of 3,000 mPa · s (B type viscometer, No. 4 rotor, 60 rpm) was prepared. did. Release this from the release paper [Asahi Roll Co., Ltd.,
Asahi release AR-148], slit thickness 15
After coating with 0 μm (liquid substance), it was dried for 3 minutes in a hot air dryer whose temperature was adjusted to 100 ° C. to form a skin layer film on the release paper. Composition of polyurethane preparation for skin layer Implaner DLV 70.0 parts by weight Implaner DLF 30.0 parts by weight Neosticker N [Nippon Kagaku Co., Ltd., thickener] 3.0 parts by weight Formlex 460 [day Hua Kagaku Co., Ltd., defoaming agent] 0.5 parts by weight Sandye Super White [Sanyo Dye Co., Ltd., water-based pigment] 15.0 parts by weight Comparative Preparation Example 1 (skin layer film for laminating) Composition shown below Then, a polyurethane preparation for the skin layer having a viscosity of 3,000 mPa · s (B-type viscometer, No. 4, rotor, 60 rpm) was prepared. Release this from the release paper [Asahi Roll Co., Ltd.,
Asahi release AR-148], slit thickness 15
After coating with 0 μm (liquid substance), it was dried for 3 minutes in a hot air dryer whose temperature was adjusted to 100 ° C. to form a skin layer film on the release paper. Composition of polyurethane preparation for skin layer Evaphanol D-5080 10.0 parts by weight Colortex White K102 [Sanyo Pigment Co., Ltd., pigment] 15.0 parts by weight Preparation Example 2 (skin preparation for coating skin layer) Mixing the components with the composition shown below, the viscosity is 7,000 mPa
A liquid preparation of s (B-type viscometer, No. 4 rotor, 60 rpm) was obtained. Composition of polyurethane preparation for skin layer Implaner DLV 70.0 parts by weight Impranil DLF 30.0 parts by weight Neo-Sticker N [Nippon Kagaku Co., Ltd., thickener] 6.0 parts by weight Formlex 460 [Nichika Chemical Co., defoamer] 0.5 parts by weight Sandye Super White [Sanyo Dye Co., Ltd., water-based pigment] 15.0 parts by weight Comparative Preparation Example 2 (skin layer polyurethane preparation for coating) Mix each component with the composition shown, and the viscosity is 8,000mPa.
A liquid preparation of s (B-type viscometer, No. 4 rotor, 60 rpm) was obtained. Composition of polyurethane preparation for skin layer Evaphanol D-5080 100.0 parts by weight Colortex White K102 [Sanyo Pigment Co., Ltd., pigment] 15.0 parts by weight

Example 1 (Production of a floor material for artificial leather with silver) A polyester non-woven fabric having a fiber thickness of 1.0 denier and a density of 0.40 g / cm ³ was used, and 300 parts by weight of an aqueous polyurethane solution A1 was added to a terminal isocyanate block product. Dispersion B 150 parts by weight, piperazine hexahydrate 20 parts by weight and water 530
The processing liquid prepared by mixing and mixing parts by weight is picked up 200
Pad treatment was performed at a weight percentage. After the treatment, wet heat drying was performed for 5 minutes with a high temperature pulper steamer adjusted to a temperature of 100 ° C. and a vapor partial pressure of 39 kPa. Next, it was washed with hot water in a warm water tank adjusted to 60 ° C. for 10 minutes, squeezed with a mangle, and then dry-heat dried with a pin tenter adjusted to 120 ° C. to obtain a flooring material for artificial leather with silver. Example 2 (Manufacture of flooring for artificial leather with silver) 300 parts by weight of polyurethane aqueous liquid A1, 150 parts by weight of terminal isocyanate block dispersion B, hydroxyethyl cellulose [Daicel Chemical Industry Co., Ltd., HEC Daicel EP500] A flooring material for artificial leather with silver was obtained in the same manner as in Example 1, except that 20 parts by weight and 530 parts by weight of water were mixed and prepared. Example 3 (Production of flooring for artificial leather with silver) 300 parts by weight of aqueous polyurethane solution A1, 150 parts by weight of terminal isocyanate block dispersion B, 20 parts by weight of piperazine hexahydrate, carboxymethylcellulose [Nichika Chemical Co., Ltd., Nikka gum C-66R] 20 parts by weight and 510 parts by weight of water were mixed to prepare a treatment solution, and a flooring material for artificial leather with silver was prepared in the same manner as in Example 1. Obtained. Example 4 (Production of flooring for artificial leather with silver) 340 parts by weight of polyurethane aqueous solution A2, 150 parts by weight of terminal isocyanate block dispersion B, 20 parts by weight of piperazine hexahydrate, carboxymethyl cellulose [Nichika Chemical Co., Ltd., Nikka gum C-66R] 20 parts by weight and 470 parts by weight of water were mixed to prepare a treatment solution, and the flooring material for artificial leather with silver was prepared in the same manner as in Example 1. Obtained. Example 5 (Production of flooring for artificial leather with silver) 300 parts by weight of polyurethane aqueous solution A1, 150 parts by weight of terminal isocyanate block dispersion B, 20 parts by weight of piperazine hexahydrate, sodium alginate [Fuji Chemical Co., Ltd. Industrial Co., Ltd., Snow Algin M] was mixed with 20 parts by weight and 510 parts by weight of water to prepare a treatment liquid, and the treatment was carried out in the same manner as in Example 1 except that a pad treatment was performed with 100% by weight of the pickup. A floor material for artificial leather with adhesive was obtained. Example 6 (Production of a floor material for artificial leather with silver) A polyester non-woven fabric having a fiber thickness of 1.0 denier and a density of 0.40 g / cm ³ was added with 300 parts by weight of an aqueous polyurethane solution A1 and a terminal isocyanate block dispersion liquid B. 150 parts by weight, ethylenediamine 6 parts by weight, starch [Nikaka Chemical Co., Ltd., Nikka gum 3A] 20 parts by weight and water 524
The processing liquid prepared by mixing and mixing parts by weight is picked up 200
Pad treatment was performed at a weight percentage. After the treatment, dry heat drying was performed for 3 minutes with a pin tenter adjusted to a temperature of 110 ° C. Then, it was washed with hot water in a warm water tank adjusted to 60 ° C. for 10 minutes, squeezed with a mangle, and then dry-heat dried with a pin tenter adjusted to 120 ° C. to obtain a floor material for artificial leather with silver. Example 7 (Production of flooring for artificial leather with silver) 100 parts by weight of aqueous polyurethane solution A1, 420 parts by weight of terminal isocyanate block dispersion B, 16.5 parts by weight of ethylenediamine, sodium polyacrylate [Sanyo Chemical Co., Ltd. Industrial Co., Ltd., Cellopol PC-300] 20
A flooring material for artificial leather with silver was obtained in the same manner as in Example 1 except that a treatment liquid prepared by mixing 44 parts by weight of water and 443.5 parts by weight of water was used. In addition, above-mentioned Example 1 and Example 3-
In the treatment liquid of No. 5, the equivalent ratio of the isocyanate group derived from the block of the terminal isocyanate block dispersion B to the imino group derived from piperazine hexahydrate was 100: 1.
72. In the treatment liquids of Examples 6 to 7, the equivalent ratio of the isocyanate group derived from the block of the terminal isocyanate block dispersion B and the amino group derived from ethylenediamine was 100: 172.

Comparative Example 1 (Production of flooring for artificial leather with silver) A polyester non-woven fabric having a fiber thickness of 1.0 denier and a density of 0.40 g / cm ³ was used as 420 parts by weight of an aqueous polyurethane liquid A1 as a migration inhibitor. Neo sticker N
Was used to prepare a flooring material for artificial leather with silver in the same manner as in Example 1 except that 10 parts by weight of water was mixed with 570 parts by weight of water to prepare a treated solution. Comparative Example 2 (Production of flooring for artificial leather with silver) A treatment liquid prepared by mixing 470 parts by weight of an aqueous polyurethane liquid A2, 10 parts by weight of Neosticker N as a migration inhibitor and 520 parts by weight of water. A flooring material for artificial leather with silver was obtained in the same manner as in Example 1 except that it was used. Comparative Example 3 (Production of flooring for artificial leather with silver) 420 parts by weight of aqueous polyurethane solution A, 10 parts by weight of Neosticker N as a migration inhibitor and 570 parts by weight of water were mixed to prepare a treatment liquid. A flooring material for artificial leather with silver was obtained in the same manner as in Example 6 except that it was used. Comparative Example 4 (Production of flooring for artificial leather with silver) Evaphanol ALS-30 was added to a polyester non-woven fabric having a fiber thickness of 1.0 denier and a density of 0.40 g / cm ³ and 500 Evaphanol.
Parts by weight, 500 parts by weight of N, N-dimethylformamide, 50 parts by weight of NK assist F-100, 50 parts by weight of NK assist F-200, 50 parts by weight of Peaklon 700 and 10 parts by weight of neosticker N. The prepared treatment liquid was pad-treated with a pickup of 230% by weight. After the treatment, water was coagulated for 10 minutes in a water tank adjusted to 25 ° C., and then washed in hot water for 20 minutes in a hot water tank adjusted to 80 ° C. Next, after squeezing with mangle, 12
Drying was carried out with a pin tenter adjusted to 0 ° C to obtain a floor material for artificial leather with silver impregnated with solvent-based polyurethane. Table 1 shows the composition of the treatment liquids used in Examples 1 to 7 and Comparative Examples 1 to 4.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

Example 8 (Production of artificial leather with silver by laminating) 100 parts by weight of Evaphanol HO-10, 7 parts by weight of Bihijuru 3100 and 2 parts by weight of Neosticker N were mixed to obtain a viscosity of 3,500 mPa · s ( A two-component aqueous polyurethane adhesive of B type viscometer, No. 4, rotor, 60 rpm) was prepared. This adhesive was coated on the skin layer side of the film obtained in Preparation Example 1 with a slit thickness of 150 μm (liquid material), dried for 2 minutes with a hot air dryer whose temperature was controlled at 100 ° C., and immediately, It was laminated with the flooring material for artificial leather with silver obtained in Example 1. Immediately after laminating, the mixture was passed through a nip roll adjusted to a temperature of 90 ° C. and a pressure of 1.96 MPa for thermocompression bonding, and then a temperature of 30 ° C. and a humidity of 40
It was aged for 2 minutes in a constant temperature and humidity room adjusted to% RH. After aging, the release paper was peeled off to obtain an artificial leather with silver. The performance of the obtained artificial leather with silver was evaluated. In the process of measuring the peel strength, the silver-coated artificial leather floor material was found to be broken, and the measurement became impossible. The peel strength at that time was 100 N / 25 mm. The texture was grade 4, and the flex resistance was grade 5. Examples 9 to 14 and Comparative Examples 5 to 7 (Production of silver-coated artificial leather by laminating) Instead of the silver-coated artificial leather flooring material obtained in Example 1, Examples 2 to 7 and Comparative Examples 1 to 1 were used. An artificial leather with silver was obtained in the same manner as in Example 8 except that the floor material for artificial leather with silver obtained in 3 was used. The performance of the obtained artificial leather with silver was evaluated.

Example 15 (Production of silver-coated artificial leather by laminating) 100 parts by weight of Neocello 10A and 2 parts of Neosticker N
Mix by weight, viscosity of 2,500 mPa · s (B type viscometer, 4
No. rotor, 60 rpm) 1-component water-based polyurethane adhesive was prepared. This adhesive is provided on the skin layer side of the skin film obtained in Preparation Example 1 with a slit thickness of 150 μm.
(Liquid substance) was coated, dried for 2 minutes with a hot air dryer controlled at 100 ° C., and immediately laminated with the floor material for artificial leather with silver obtained in Example 1. Immediately after laminating, it is passed through a nip roll adjusted to a temperature of 90 ° C. and a pressure of 1.96 MPa to be thermocompression bonded, and then a temperature of 30
It was aged for 2 days in a constant temperature and constant humidity chamber adjusted to 40 ° C. and a humidity of 40% RH. After aging, the release paper was peeled off to obtain an artificial leather with silver. The performance of the obtained artificial leather with silver was evaluated.
During the process of measuring the peel strength, destruction of the artificial leather floor material with silver was observed, and the measurement became impossible. The peel strength at that time was 87.
It was N / 25 mm. The texture was grade 4, and the flex resistance was grade 5. Examples 16 to 21 and Comparative Examples 8 to 10 (production of artificial leather with silver by laminating) Instead of the floor material for artificial leather with silver obtained in Example 1, Examples 2 to 7 or Comparative Examples 1 to 1 An artificial leather with silver was obtained in the same manner as in Example 15 except that the floor material for artificial leather with silver obtained in 3 was used. The performance of the obtained artificial leather with silver was evaluated. Comparative Example 11 (Production of artificial leather with silver using a two-component solvent-based polyurethane adhesive) 100 parts by weight of Neocello 150 and 3 parts by weight of Coronate L were mixed to give a viscosity of 5,000 mPa · s (B-type viscometer, A two-component solvent-based polyurethane adhesive (No. 4 rotor, 60 rpm) was prepared. This adhesive is provided on the skin layer side of the skin layer film obtained in Comparative Preparation Example 1 with a slit thickness of 150 μm.
(Liquid substance) was coated and dried for 2 minutes by a hot air dryer whose temperature was controlled at 100 ° C., and immediately laminated with the floor material for artificial leather with silver obtained in Comparative Example 4.
Immediately after the lamination, it was passed through a nip roll adjusted to a temperature of 90 ° C. and a pressure of 1.96 MPa for thermocompression bonding, and then aged in a constant temperature and constant humidity chamber adjusted to a temperature of 30 ° C. and a humidity of 40% RH for 2 days. After aging, the release paper was peeled off to obtain an artificial leather with silver. The performance of the obtained artificial leather with silver was evaluated. In the process of measuring the peel strength, the silver-coated artificial leather floor material was found to be broken, and the measurement became impossible. The peel strength at that time was 85 N / 25 mm. Also, the texture and flex resistance are
Both were 5th grade. Examples 8-21 and Comparative Examples 5-1
The results of No. 1 are shown in Table 2.

[0039]

[Table 4]

[0040]

[Table 5]

As shown in Table 2, in addition to the (A) polyurethane aqueous liquid, (B) urethane prepolymer-terminated isocyanate blocked product of the present invention, (C) polyamine compound and / or (D) water-soluble organic compound Based on the flooring materials of Examples 1 to 7 produced by using a polymer, the artificial leather with silver obtained by dry lamination is prepared by using the two-pack type aqueous polyurethane adhesive as in Examples 8 to 14. Example 15
Even if a one-component type aqueous polyurethane adhesive as described in No. 21 is used, a peel strength large enough to cause the floor material to be broken is obtained, the texture and flexibility are excellent, and the floor is manufactured using a solvent-based polyurethane resin. It can be seen that the material has a performance comparable to that of the floor material for artificial leather with silver of Comparative Example 11 obtained from the material and the skin layer film. On the other hand, based on the flooring materials of Comparative Examples 1 to 3 produced by using only the (A) polyurethane aqueous solution and a thickener, the artificial leather with silver obtained by dry lamination is When a two-component water-based polyurethane adhesive as in Example 7 is used, a large peeling strength that causes the floor material to be broken is obtained, but the texture and flexibility are inferior, and the one-component water-based adhesive as in Comparative Examples 8 to 10 is used. When a polyurethane adhesive is used, the adhesive and the flooring material are separated by interfacial fracture, resulting in low adhesive strength and poor texture and flex resistance.

Example 22 (Production of silver-coated artificial leather by coating) The surface layer polyurethane preparation prepared in Preparation Example 2 was slit on the silver-coated artificial leather flooring material obtained in Example 1. The silver-coated artificial leather was coated with a thickness of 200 μm (liquid substance) and dried for 2 minutes with a hot air dryer whose temperature was adjusted to 100 ° C. The performance of the obtained artificial leather with silver was evaluated. In the process of measuring the peel strength, the silver-coated artificial leather floor material was broken, and the measurement became impossible. The peel strength at that time was 98 N / 25 mm. Also, the texture is grade 4,
Flex resistance was grade 5. Examples 23 to 28 and Comparative Examples 12 to 14 (Production of silver-coated artificial leather by coating) Instead of the silver-coated artificial leather flooring material obtained in Example 1, Examples 2 to 7 or Comparative Examples 1 to 1 were used. An artificial leather with silver was obtained in the same manner as in Example 22 except that the floor material for artificial leather with silver obtained in 3 was used. The performance of the obtained artificial leather with silver was evaluated. Comparative Example 15 Instead of the skin layer polyurethane preparation obtained in Preparation Example 2, the skin layer polyurethane preparation obtained in Comparative Preparation Example 2 was used, and the silver-coated artificial leather flooring material obtained in Example 1 was used. A silver-coated artificial leather made of a conventional solvent-based polyurethane resin was obtained in the same manner as in Example 22 except that the silver-coated artificial leather flooring material obtained in Comparative Example 4 was used instead of. The performance of the obtained artificial leather with silver was evaluated. The results of Examples 22 to 28 and Comparative Examples 12 to 15 are shown in Table 3.

[0043]

[Table 6]

As shown in Table 3, in addition to the (A) polyurethane aqueous solution, (B) urethane prepolymer-terminated isocyanate blocked product of the present invention, (C) polyamine compound and / or (D) water-soluble organic compound Based on the flooring materials of Examples 1 to 7 produced by using the polymer, the artificial leather with silver obtained by the coating process has a large peeling strength enough to cause the flooring material to break, and has a good texture and flexibility. It is also found that it has excellent performance and is equivalent in performance to the artificial leather with silver of Comparative Example 15 obtained from the conventional solvent-based polyurethane resin. On the other hand, (A)
Although the artificial leather with silver of Comparative Examples 12 to 14 based on the flooring material produced by using only the aqueous polyurethane liquid and the thickener, the peeling strength enough to cause the flooring material to break is obtained. The peel strength is slightly smaller than that of the artificial leather with silver of the invention, and the texture and flex resistance are inferior.

[0045]

EFFECTS OF THE INVENTION By using the flooring material for artificial leather with silver produced by the method of the present invention, even if a skin layer or an adhesive of an aqueous polyurethane resin, which has been problematic in terms of performance, is used,
It is possible to obtain a synthetic leather with silver that is excellent in peel strength, texture and flex resistance. The artificial leather with silver of the present invention is comparable to the artificial leather with silver obtained from the conventional solvent-based polyurethane resin, and it is not necessary to use a solvent substantially and can be replaced by an aqueous resin. is there. As a result, it is possible to solve problems such as air pollution and water pollution due to the solvent discharged during processing, labor for collecting the solvent, and working environment of workers.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichi Umeya             Fukui City Fukui Prefecture Bunkyo 4-23-1 Nikkaka             Gaku Co., Ltd. F term (reference) 4F055 AA03 AA12 BA13 DA08 DA13                       EA04 EA24 FA18 FA39 GA03                       HA17

Claims (7)

[Claims] 1. In addition to (A) an aqueous polyurethane solution and (B) a urethane prepolymer-terminated isocyanate block product, at least one selected from the group consisting of (C) polyamine compounds and (D) water-soluble organic polymers. A method for producing a flooring material for artificial leather with silver, comprising impregnating a base material with a mixed solution containing the material, and then drying. 2. A polyurethane aqueous solution (A), wherein an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate and a polyol is emulsified and dispersed in water using a nonionic surfactant of HLB 7 to 16. The method for producing a flooring material for artificial leather with silver according to claim 1, which is obtained by a chain extension reaction with a polyamine compound having two or more amino groups and / or imino groups. 3. A neutralized product of an isocyanate group-terminated prepolymer obtained by reacting (A) an aqueous polyurethane solution with a polyisocyanate, a polyol, and a compound having an anionic hydrophilic group and two or more active hydrogens, The method for producing a flooring material for artificial leather with silver according to claim 1, which is obtained by emulsifying and dispersing in water and then subjecting the polyamine compound having two or more amino groups and / or imino groups to a chain extension reaction. 4. The method for producing a flooring material for artificial leather with silver according to claim 1, wherein the urethane prepolymer-terminated isocyanate block product (B) is a bisulfite-terminated isocyanate block product. 5. The polyamine compound (C) is a compound having two or more amino groups and / or imino groups.
A method for producing the floor material for artificial leather with silver as described above. 6. The water-soluble organic polymer (D) is at least one polymer selected from the group consisting of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, sodium alginate, sodium polyacrylate and starch. The method for producing a floor material for artificial leather with silver according to claim 1. 7. A floor material for artificial leather with silver obtained by the method according to claim 1, which is obtained by laminating or coating a skin layer. Artificial leather with silver.