JP3989727B2 - Manufacturing method of flooring material for artificial leather with silver and artificial leather with silver - Google Patents

Description

【００３５】
【表２】

【００３６】
【表３】

【００３７】
参考例８（ラミネート加工による銀付人工皮革の製造）
エバファノールＨＯ−１０を１００重量部、バイヒジュール３１００を７重量部及びネオステッカーＮを２重量部混合し、粘度３,５００ｍＰａ・ｓ（Ｂ型粘度計、４号ローター、６０ｒｐｍ）の２液型水性ポリウレタン系接着剤を調液した。
この接着剤を、調製例１で得られたフイルムの表皮層側に、スリット厚さ１５０μｍ（液状物）でコーティングし、１００℃に温調された熱風乾燥機にて２分間乾燥させ、直ちに、参考例１で得られた銀付人工皮革用床材とのラミネートを行った。ラミネート後、直ちに、温度９０℃、圧力１.９６ＭＰａに調整したニップロールに通し熱圧着させ、次いで、温度３０℃、湿度４０％ＲＨに調整した恒温恒湿室で２日間熟成させた。熟成後、離型紙を剥がして銀付人工皮革を得た。
得られた銀付人工皮革について、性能を評価した。剥離強度の測定の過程で、銀付人工皮革用床材の破壊が見られ、測定不能となり、その時点での剥離強度は１００Ｎ／２５ｍｍであった。また、風合いは４級であり、耐屈曲性は５級であった。
参考例９及び実施例１０〜１４及び比較例５〜７（ラミネート加工による銀付人工皮革の製造)
参考例１で得られた銀付人工皮革用床材の代わりに、参考例２及び実施例３〜７及び比較例１〜３で得られた銀付人工皮革用床材を用いた以外は、参考例８と同様にして銀付人工皮革を得た。得られた銀付人工皮革について、性能を評価した。
【００３８】
参考例１５（ラミネート加工による銀付人工皮革の製造）
ネオセロ１０Ａを１００重量部とネオステッカーＮを２重量部混合し、粘度２,５００ｍＰａ・ｓ（Ｂ型粘度計、４号ローター、６０ｒｐｍ）の１液型水性ポリウレタン系接着剤を調液した。
この接着剤を、調製例１で得られた表皮層フイルムの表皮層側に、スリット厚さ１５０μｍ（液状物）でコーティングし、１００℃に温調された熱風乾燥機にて２分間乾燥させ、直ちに、参考例１で得られた銀付人工皮革用床材とのラミネートを行った。ラミネート後、直ちに、温度９０℃、圧力１.９６ＭＰａに調整したニップロールに通し熱圧着させ、次いで、温度３０℃、湿度４０％ＲＨに調整した恒温恒湿室で２日間熟成させた。熟成後、離型紙を剥がして銀付人工皮革を得た。
得られた銀付人工皮革について、性能を評価した。剥離強度の測定の過程で、銀付人工皮革用床材の破壊が見られ、測定不能となり、その時点での剥離強度は８７Ｎ／２５ｍｍであった。また、風合いは４級であり、耐屈曲性は５級であった。
参考例１６及び実施例１７〜２１及び比較例８〜１０（ラミネート加工による銀付人工皮革の製造）
参考例１で得られた銀付人工皮革用床材の代わりに、参考例２及び実施例３〜７又は比較例１〜３で得られた銀付人工皮革用床材を用いた以外は、参考例１５と同様にして銀付人工皮革を得た。得られた銀付人工皮革について、性能を評価した。
比較例１１（２液型溶剤系ポリウレタン接着剤を用いた銀付人工皮革の製造）
ネオセロ１５０を１００重量部とコロネートＬを３重量部混合し、粘度５,０００ｍＰａ・ｓ（Ｂ型粘度計、４号ローター、６０ｒｐｍ）の２液型溶剤系ポリウレタン接着剤を調液した。
この接着剤を、比較調製例１で得られた表皮層フイルムの表皮層側に、スリット厚さ１５０μｍ（液状物）でコーティングし、１００℃に温調されている熱風乾燥機にて２分間乾燥させ、直ちに、比較例４で得られた銀付人工皮革用床材とのラミネートを行った。ラミネート後、直ちに、温度９０℃、圧力１.９６ＭＰａに調整したニップロールに通し熱圧着させ、次いで、温度３０℃、湿度４０％ＲＨに調整した恒温恒湿室で２日間熟成させた。熟成後、離型紙を剥がして銀付人工皮革を得た。
得られた銀付人工皮革について、性能を評価した。剥離強度の測定の過程で、銀付人工皮革用床材の破壊が見られ、測定不能となり、その時点での剥離強度は８５Ｎ／２５ｍｍであった。また、風合いと耐屈曲性は、ともに５級であった。
参考例８、９、実施例１０〜１４、参考例１５、１６、実施例１７〜２１及び比較例５〜１１の結果を、第２表に示す。
【００３９】
【表４】

【００４０】
【表５】

【００４１】
第２表に見られるように、本発明の(Ａ)ポリウレタン水性液、(Ｂ)ウレタンプレポリマー末端イソシアネートブロック物に加えて、(Ｃ)ポリアミン化合物及び／又は(Ｄ)水溶性有機高分子を用いて製造した参考例１、２及び実施例３〜７の床材をもとに、ドライラミネーション加工により得られる銀付人工皮革は、参考例８、９及び実施例１０〜１４のように２液型水性ポリウレタン接着剤を用いても、参考例１５、１６及び実施例１７〜２１のように１液型水性ポリウレタン接着剤を用いても、床材破壊が発生するほどの大きい剥離強度が得られ、風合いと屈曲性にも優れ、溶剤系ポリウレタン樹脂を用いて製造した床材と表皮層フイルムとから得られる比較例１１の銀付人工皮革用床材と遜色ない性能を有することが分かる。
これに対して、(Ａ)ポリウレタン水性液と増粘剤のみを用いて製造した比較例１〜３の床材をもとに、ドライラミネーション加工により得られる銀付人工皮革は、比較例５〜７のように２液型水性ポリウレタン接着剤を用いると、床材破壊が発生するほどの大きい剥離強度が得られるが、風合いと屈曲性が劣り、比較例８〜１０のように１液型水性ポリウレタン接着剤を用いると、接着剤と床材とは界面破壊により剥離して接着強度が小さく、風合いと耐屈曲性にも劣っている。
【００４２】
参考例２２（コーティング加工による銀付人工皮革の製造）
調製例２で得られた表皮層ポリウレタン調液物を、参考例１で得られた銀付人工皮革用床材上に、スリット厚さ２００μｍ（液状物）でコーティングし、１００℃に温調された熱風乾燥機にて２分間乾燥させて銀付人工皮革を得た。
得られた銀付人工皮革について、性能を評価した。剥離強度の測定の過程で、銀付人工皮革用床材の破壊が見られ、測定不能となり、その時点での剥離強度は９８Ｎ／２５ｍｍであった。また、風合いは４級であり、耐屈曲性は５級であった。
参考例２３及び実施例２４〜２８及び比較例１２〜１４（コーティング加工による銀付人工皮革の製造）
参考例１で得られた銀付人工皮革用床材の代わりに、参考例２及び実施例３〜７又は比較例１〜３で得られた銀付人工皮革用床材を用いた以外は、参考例２２と同様にして銀付人工皮革を得た。得られた銀付人工皮革について、性能を評価した。
比較例１５
調製例２で得られた表皮層ポリウレタン調液物の代わりに比較調製例２で得られた表皮層ポリウレタン調液物を用い、参考例１で得られた銀付人工皮革用床材の代わりに比較例４で得られた銀付人工皮革用床材を用いた以外は、参考例２２と同様にして、従来の溶剤系ポリウレタン樹脂からなる銀付人工皮革を得た。得られた銀付人工皮革について、性能を評価した。
参考例２２、２３及び実施例２４〜２８及び比較例１２〜１５の結果を、第３表に示す。
【００４３】
【表６】

【００４４】
第３表に見られるように、本発明の(Ａ)ポリウレタン水性液、(Ｂ)ウレタンプレポリマー末端イソシアネートブロック物に加えて、(Ｃ)ポリアミン化合物及び／又は(Ｄ)水溶性有機高分子を用いて製造した参考例１、２及び実施例３〜７の床材をもとに、コーティング加工により得られる銀付人工皮革は、床材破壊が発生するほどの大きい剥離強度が得られ、風合いと屈曲性にも優れ、従来の溶剤系ポリウレタン樹脂から得られる比較例１５の銀付人工皮革と同等の性能を有することが分かる。
一方、(Ａ)ポリウレタン水性液と増粘剤のみを用いて製造した床材をもとにした比較例１２〜１４の銀付人工皮革は、床材破壊が発生するほどの剥離強度が得られているが、本発明の銀付人工皮革と比較する剥離強度がやや小さく、また、風合いと耐屈曲性が劣っている。
【００４５】
【発明の効果】
本発明方法により製造された銀付人工皮革用床材を用いると、これまでは性能の面で問題のあった水性ポリウレタン樹脂の表皮層や接着剤を用いても、剥離強度、風合い、耐屈曲性に優れた銀付人工皮革を得ることができる。本発明の銀付人工皮革は、従来の溶剤系ポリウレタン樹脂から得られる銀付人工皮革に比べて遜色のないものであり、実質的に溶剤を使用する必要がなく、水性樹脂による代替が可能である。その結果、加工中に排出される溶剤による大気汚染や水質汚濁、溶剤の回収労力、及び、作業者の労働環境などの問題を解消することが可能となる。[0001]
BACKGROUND 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 processing a flooring material that gives an artificial leather with silver excellent in texture, peel strength and flex resistance, and by processing the skin layer on the flooring material obtained by the manufacturing method. It relates to artificial leather with silver.
[0002]
[Prior art]
Conventionally, as a method of manufacturing artificial leather with silver, the polyurethane resin skin layer formed on the release paper by dry method is coated with an adhesive and dried, and then bonded to the floor material impregnated with polyurethane resin. The dry lamination method, also the polyurethane resin skin layer is coated with an adhesive, and the wet lamination method is applied to the floor material impregnated with polyurethane resin. The polyurethane resin that forms the skin layer is coated on the floor material impregnated with polyurethane resin. There are known dry coating processes for drying, wet coating processes in which a polyurethane resin as a skin layer is coated on a floor material impregnated with a polyurethane resin, and then water coagulation is performed. Among these methods, dry lamination, dry coating, and wet coating are often used in terms of production stability of artificial leather with silver and quality such as texture.
Polyurethane resins used in these processes include solvent-based polyurethane resins, that is, organic solvents such as N, N-dimethylformamide, toluene, and methyl ethyl ketone, for flooring impregnation, skin layers, and adhesives. Polyurethane resin dissolved in is often used. However, using a solvent-based polyurethane resin can provide artificial leather with silver excellent in texture, peel strength, and bending resistance, but there are concerns about the working environment and there are solvents that are harmful during processing. Since the wastewater and exhaust gas are mixed and discharged, a great deal of labor and cost are required for the recovery process for preventing water pollution and air pollution.
Therefore, as an alternative to solvent-based polyurethane resins, water-based polyurethane resins for floor material impregnation and skin layers have been investigated, but compared to artificial leather with silver using solvent-based polyurethane resins, the texture and peeling It is inferior in terms of strength and bending resistance, and has not been put into practical use.
In addition, two-component water-based polyurethane adhesives composed of water-dispersed polyisocyanates and urethane polyols have been studied as adhesives for silver-coated artificial leather with excellent peel strength. It is inadequate for products that require strength, and its use is limited at present.
[0003]
[Problems to be solved by the invention]
The present invention is a flooring material capable of obtaining an artificial leather with silver excellent in texture, peel strength, flex resistance, a method for producing a flooring material for artificial leather with silver using an aqueous polyurethane resin, and An object of the present invention is to provide an artificial leather with silver obtained by laminating or coating a skin layer on a floor material obtained by the production method.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have obtained a mixed liquid containing a polyamine compound or a water-soluble organic polymer in addition to a polyurethane aqueous solution and a urethane prepolymer-terminated isocyanate block product as a base material. It was found that the artificial leather with silver produced using the floor material obtained by impregnating and drying was found to be excellent in texture, peel strength and bending resistance, and based on this finding, the present invention was completed. It came.
That is, the present invention
(1) In addition to (A) aqueous polyurethane liquid and (B) urethane prepolymer-terminated isocyanate blocked product, a base material was impregnated with a mixed liquid containing (C) a polyamine compound and (D) a water-soluble organic polymer. Then, a method for producing a flooring material for artificial leather with silver, characterized by drying,
(2) (A) An aqueous polyurethane liquid is obtained by emulsifying and dispersing an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate and a polyol with water using a nonionic surfactant of HLB7-16, The method for producing a flooring material for artificial leather with silver according to claim 1, which is obtained by chain elongation reaction with a polyamine compound having two or more groups and / or imino groups,
(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. The method for producing a flooring material for artificial leather with silver according to claim 1, which is obtained by chain elongation reaction using a polyamine compound having two or more amino groups and / or imino groups after emulsification and dispersion;
(4) (B) The method for producing a flooring for artificial leather with silver according to item 1, wherein the urethane prepolymer terminal isocyanate block is a terminal isocyanate block with bisulfite,
(5) (C) The method for producing a flooring material for artificial leather with silver according to item 1, wherein the polyamine compound is a compound having two or more amino groups and / or imino groups,
(6) (D) The water-soluble organic polymer is at least one polymer selected from the group consisting of methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, sodium alginate, sodium polyacrylate, and starch. The method for producing a flooring material for artificial leather with silver according to item 1, and
(7) Silver-attached, obtained by laminating or coating a skin layer on a flooring for artificial leather with silver obtained by the production method according to any one of items 1 to 6 Artificial leather,
Is to provide.
Furthermore, as a preferred embodiment of the present invention,
(8) The first aspect, wherein the weight ratio of (A) aqueous polyurethane liquid and (B) urethane prepolymer-terminated isocyanate block product in terms of solid content is (A) :( B) = 100: 500 to 100: 1. Manufacturing method for flooring for artificial leather with silver,
(9) The equivalent ratio of the isocyanate group regenerated from the (B) urethane prepolymer terminal isocyanate blocked product and the total of the amino group, imino group and nitrilo group of the (C) polyamine compound is 100: 300 to 100: 30. A method for producing a flooring material for artificial leather with silver according to Item 1, and
(10) The weight of the resin derived from the (A) aqueous polyurethane 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. The manufacturing method of the flooring material for artificial leather with silver of 1 description,
Can be mentioned.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the method for producing a flooring for artificial leather with silver according to the present invention, in addition to (A) aqueous polyurethane liquid and (B) urethane prepolymer-terminated isocyanate block, (C) polyamine compound and (D) water-soluble organic high The substrate is impregnated with a mixed solution containing at least one selected from the group consisting of molecules, and then dried.
In the method of the present invention, as a base material used for production of a flooring material for artificial leather with silver, a base material generally used for artificial leather can be used without particular limitation, for example, non-woven fabric, woven fabric, knitted fabric, etc. Can be mentioned. Among these base materials, a nonwoven fabric using polyamide fiber, acrylic fiber or polyester fiber can be suitably used because it provides a quality such as a texture close to natural leather. The thickness of the fibers constituting the nonwoven fabric is preferably 2.5 denier or less, and more preferably 2 denier or less. If the fiber thickness 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 be lowered. Moreover, the density of the nonwoven fabric is 0.2 to 0.7 g / cm. ^Three Preferably, it is 0.35-0.55 g / cm ^Three It is more preferable that Nonwoven fabric density is 0.2 g / cm ^Three If it is less than 1, the peel strength between the skin layer and the flooring material for artificial leather with silver may be lowered. The density of the nonwoven fabric is 0.7 g / cm ^Three If it exceeds 1, the texture of the artificial leather with silver becomes coarse and hard, the quality is impaired, and the flex resistance may be lowered.
[0006]
In the method of the present invention, as the polyurethane aqueous liquid (A), an aqueous liquid obtained by emulsifying, dispersing or solubilizing a polyurethane resin in water can be used. Among these, a forced emulsification type polyurethane aqueous solution emulsified and dispersed using an emulsifier and a self-emulsification type polyurethane aqueous solution that can be emulsified and dispersed without using an emulsifier can be suitably used.
The forced emulsification type polyurethane aqueous liquid is obtained by emulsifying and dispersing an isocyanate group-terminated prepolymer obtained by reacting (a) polyisocyanate and (b) polyol in water using a nonionic surfactant of HLB7-16. Thereafter, (c) an aqueous liquid of a polyurethane resin obtained by chain extension reaction with a polyamine compound having two or more amino groups and / or imino groups. In the method of the present invention, HLB refers to a value calculated by the Griffin equation.
The self-emulsifying polyurethane aqueous liquid is an isocyanate group-terminated prepolymer obtained by reacting (a) a polyisocyanate, (b) a polyol, and (d) a compound having an anionic hydrophilic group and two or more active hydrogens. An aqueous solution of a polyurethane resin obtained by emulsifying and dispersing a neutralized product in water, and then (c) chain-extending reaction using a polyamine compound having two or more amino groups and / or imino groups.
[0007]
In the method of the present invention, as the polyisocyanate (a), an aromatic polyisocyanate having two or more isocyanate groups, an aliphatic polyisocyanate and an alicyclic polyisocyanate can be used without particular limitation. Isocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate and other aromatic polyisocyanates, hexamethylene diisocyanate and other aliphatic polyisocyanates, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3-bis ( And alicyclic polyisocyanates such as isocyanatomethyl) cyclohexane.
Among these, the aliphatic isocyanate or alicyclic polyisocyanate can be suitably used because the obtained polyurethane aqueous liquid (A) is non-yellowing, and can be used preferably. Hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane Diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane can be particularly preferably used. (a) Polyisocyanate can be used individually by 1 type, or can also be used in combination of 2 or more type.
[0008]
In the method of the present invention, as the (b) polyol, polyester polyol, polycarbonate polyol and polyether polyol having two or more hydroxyl groups can be suitably used. The average molecular weight of the polyol is preferably 500 to 4,000, and more preferably 700 to 3,000.
Examples of the polyester polyol include 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, polycondensation product of 1,6-hexanediol and dimer acid, copolycondensation product of 1,6-hexanediol, adipic acid and dimer acid, nonanediol and dimer acid And polycondensates of ethylene glycol, dimer acid, and copolycondensates of ethylene glycol, adipic acid and dimer acid.
Examples of the polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, and poly-1,4-cyclohexanedimethylene carbonate diol.
Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, ethylene oxide and butylene oxide random copolymers, and block copolymers. Furthermore, a polyether polyester polyol having an ether bond and an ester bond can also be used.
These polyols can be used alone or in combination of two or more.
[0009]
In the method of the present invention, (d) the compound having an anionic hydrophilic group and two or more active hydrogens used for producing the self-emulsifying polyurethane aqueous liquid is not particularly limited, but the anionic hydrophilic group is a carboxyl group, A compound in which the active hydrogen is a 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. Moreover, the polyester polyol which has a pendant carboxyl group obtained by making dicarboxylic acid, such as aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid, react with the diol which has a carboxyl group can also be used. In the reaction, a diol having no carboxyl group can be mixed with a diol having a carboxyl group. These (d) compounds having an anionic hydrophilic group and two or more active hydrogens can be used singly or in combination of two or more.
In the self-emulsifying type polyurethane aqueous solution, the neutralized product of the isocyanate group-terminated prepolymer is before or after the synthesis of the isocyanate group-terminated prepolymer using the components (a), (b) and (d). Then, the neutralized product obtained by neutralizing the anionic hydrophilic group of the component (d). There are no particular restrictions on the compound used for neutralizing the anionic hydrophilic group, for example, amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, sodium hydroxide, potassium hydroxide, ammonia And so on.
[0010]
In the 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 based on the weight of the polyurethane resin, and 0.5 to 2 More preferably, it is 0.0% by weight. 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. If the content of the anionic hydrophilic group exceeds 4.5% by weight, the water resistance of the polyurethane resin may be lowered.
When the above components are used to synthesize an isocyanate group-terminated prepolymer, that is, a urethane prepolymer having an isocyanate group at the end, (e) a chain extender can be used as necessary. Examples of (e) chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and sorbitol. A chain extender can be used individually by 1 type, or can also be used in combination of 2 or more type. There is no restriction | limiting in particular in the manufacturing method of an isocyanate group terminal prepolymer, For example, it can manufacture by the conventionally well-known one-stage type what is called a one-shot method, a multistage isocyanate polyaddition reaction method, etc. The reaction temperature is preferably 40 to 150 ° C.
[0011]
In the method of the present invention, when the isocyanate group-terminated prepolymer of the forced emulsification type polyurethane aqueous liquid is emulsified and dispersed in water, it is preferable to use a nonionic surfactant of HLB7-16, and a nonionic surfactant of HLB9-15. It is more preferable to use an agent. When the HLB is less than 7, it is difficult to emulsify and disperse the prepolymer, and even when dispersible, the stability may be inferior. If the HLB exceeds 16, it is difficult to emulsify and disperse the prepolymer, and the water resistance of the resulting polyurethane resin may be inferior even when dispersible.
The structure of the nonionic surfactant to be used is not particularly limited. For example, polyoxyethylene distyryl phenyl ether type nonionic surfactant, polyoxyethylene propylene distyryl phenyl ether type nonionic surfactant, polyoxyethylene trioxide Examples 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 individually by 1 type, or can also be used in combination of 2 or more type.
The amount of these nonionic surfactants to be 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 an isocyanate group-terminated prepolymer. The amount is preferably 0.5 to 10 parts by weight, more preferably 1 to 6 parts by weight with respect to 100 parts by weight. If the amount of the nonionic surfactant used is less than 0.5 parts by weight based on 100 parts by weight of the isocyanate group-terminated prepolymer, it may be difficult to obtain a stable emulsified dispersion state. When the usage-amount of a nonionic surfactant exceeds 10 weight part with respect to 100 weight part of isocyanate group terminal prepolymers, there exists a possibility that the water resistance of the polyurethane resin obtained may fall.
In the self-emulsifying polyurethane aqueous liquid, the neutralized product of the isocyanate group-terminated prepolymer can be emulsified and dispersed in water without adding an emulsifier. If necessary, a nonionic surfactant of HLB 7 to 16 can be used. Can be used.
[0012]
In the method of the present invention, when the isocyanate group-terminated prepolymer or the neutralized product of the isocyanate group-terminated prepolymer is emulsified and dispersed in water, it is preferable to use mechanical shearing force in order to cause phase inversion emulsification. There is no restriction | limiting in particular in the emulsification apparatus which gives a mechanical shearing force, For example, a homomixer, a homogenizer, etc. can be mentioned. The isocyanate group-terminated prepolymer or the neutralized product of the isocyanate group-terminated prepolymer is emulsified and dispersed in water at a temperature ranging from room temperature to 40 ° C., thereby minimizing the reaction between the isocyanate group and water or a nonionic surfactant. Is preferred. Furthermore, reaction inhibitors such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, and benzoyl chloride can be added as necessary.
In the method of the present invention, after an isocyanate group-terminated prepolymer or a neutralized product of an 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 elongation reaction is carried out to obtain an aqueous polyurethane liquid. (c) Examples of the compound having two or more amino groups and / or imino groups include ethylenediamine, tetramethylenediamine, hexamethylenediamine, hydrazine, piperazine, isophoronediamine, norbornanediamine, diaminodiphenylmethane, tolylenediamine, 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 can be used individually by 1 type, or can also be used in combination of 2 or more type.
The chain extension reaction of the isocyanate group-terminated prepolymer or the neutralized product of the isocyanate group-terminated prepolymer can be carried out by adding the (c) polyamine compound to the emulsified dispersion of these prepolymers, or (c) the polyamine It can also be carried out by adding an emulsified dispersion of a prepolymer to the compound. The chain extension reaction is preferably performed at a reaction temperature of 20 to 40 ° C., and is usually completed in 30 to 120 minutes.
[0013]
The (B) urethane prepolymer terminal isocyanate blocked product used in the method of the present invention is a urethane prepolymer having hydrophilicity and thermal reactivity, and is a compound in which the terminal isocyanate group is blocked with a blocking agent. The urethane prepolymer-terminated isocyanate block product can be stored for a long time in the state of an aqueous solution. The blocking agent is desorbed by heating to regenerate active isocyanate groups, and polyaddition reaction within or between urethane prepolymer molecules. To give a polyurethane polymer, or an addition reaction with other functional groups. The desorption temperature of the blocking agent is preferably 50 to 150 ° C.
The urethane prepolymer-terminated isocyanate block product comprises (f) a compound having two or more active hydrogens, (g) a polyisocyanate compound having two or more isocyanate groups, and (h) two or more compounds as required. It can be produced by blocking a terminal isocyanate group of a urethane prepolymer obtained by reacting a chain extender having active hydrogen with a blocking agent.
[0014]
(f) Examples of the compound having two or more active hydrogens include compounds having two or more hydroxyl groups, carboxyl groups, amino groups, mercapto groups, etc. in the terminal or molecule. Polyester, polyether ester, polycarbonate and the like can be suitably used. Examples of the polyether include homopolymers such as ethylene oxide, propylene oxide, styrene oxide, and epichlorohydrin, random or block copolymers, and addition polymers to polyhydric alcohols. Examples of the polyester and polyether ester include polyvalent saturated carboxylic acids such as adipic acid, succinic acid, phthalic acid, and maleic anhydride, unsaturated carboxylic acids or acid anhydrides thereof, ethylene glycol, diethylene glycol, 1, Polyalkylene ether glycols such as 4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane and other polysaturated alcohols, unsaturated alcohols, relatively low molecular weight polyethylene glycols and polypropylene glycols, or the like Polyesters obtained mainly from linear or branched condensation products obtained from mixtures of the above, polyesters obtained from lactones or hydroxy acids, and polyesters prepared in advance to which ethylene oxide, propylene oxide, etc. are added. And the like ether esters.
[0015]
(g) As the polyisocyanate, aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate having two or more isocyanate groups can be used without particular limitation. For example, tolylene diisocyanate, xylylene diisocyanate , Tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, aromatic polyisocyanate such as naphthalene diisocyanate, aliphatic polyisocyanate such as hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane And alicyclic polyisocyanates.
Among these, aliphatic isocyanate or alicyclic polyisocyanate can be suitably used because the obtained (B) urethane prepolymer-terminated isocyanate block is non-yellowing, and can be suitably used. Hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl Methane diisocyanate, norbornane diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane can be particularly preferably used. (g) Polyisocyanate can be used individually by 1 type, or can also be used in combination of 2 or more type.
(h) Examples of the chain extender 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 polyhydric alcohols such as ethylenediamine, hexamethylenediamine and piperazine, amino alcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol, and water.
[0016]
(f) a compound having two or more active hydrogens, (g) a polyisocyanate compound having two or more isocyanate groups, and (h) a chain extender having two or more active hydrogens as required. There is no particular limitation on the method for producing the urethane prepolymer, and for example, it can be produced by a conventionally known one-stage so-called one-shot method, multi-stage isocyanate polyaddition reaction method, or the like. Although there is no restriction | limiting in particular in reaction conditions, It is preferable that reaction temperature is 150 degrees C or less, and it is more preferable that it is 50-120 degreeC. The reaction time is usually 5 minutes to several hours.
In addition, the molar ratio of isocyanate group / active hydrogen is 1 or more, but since a blocked isocyanate structure having thermal reactivity is required, it is essential that free isocyanate groups remain in the obtained urethane prepolymer. It is. The content of free isocyanate groups is preferably 1 to 10% by weight, and more preferably 2 to 7% by weight. Even if the content of free isocyanate groups is less than 1% by weight or more than 10% by weight, the water solubility of the resulting urethane prepolymer-terminated isocyanate block becomes unstable, and is separated and gelated over time. There is a risk.
[0017]
The blocking agent for the urethane prepolymer terminal isocyanate blocked product used in the method of the present invention is one that reacts with the terminal isocyanate group, is hydrophilic, and can be easily released under the conditions of thermal reaction to regenerate the active isocyanate group. If there is no particular limitation, for example, bisulfite, oxime, alcohol and the like can be mentioned. Among these, bisulfite can be particularly preferably used because of its low desorption temperature. Since the reaction between the urethane prepolymer and the aqueous bisulfite solution is an exothermic reaction, which is a competitive reaction between bisulfite and water, the reaction temperature is required to selectively block the bisulfite sufficiently. Is preferably 50 ° C. or lower, more preferably 20 to 40 ° C. The reaction time is preferably 5 minutes to 2 hours. After completion of the reaction, it is diluted with water to an appropriate concentration to obtain a hydrophilic and heat-reactive urethane prepolymer-terminated isocyanate block product. This block product can be stored for a long time in the state of an aqueous solution, and when heated to 50 to 150 ° C., the bisulfite of the blocking agent dissociates to regenerate active isocyanate groups. A polymerization addition reaction occurs between molecules to form a polyurethane polymer, or addition to another functional group.
[0018]
The (C) polyamine compound 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) Examples of the polyamine compound include ethylenediamine, tetramethylenediamine, hexamethylenediamine, hydrazine, piperazine, isophoronediamine, norbornanediamine, diaminodiphenylmethane, tolylenediamine, xylylenediamine, triethylenediamine, diethylenetriamine, triethylenetetramine, Examples thereof include tetraethylenepentamine, iminobispropylamine, and tetramethylhexamethylenediamine. Among these, a compound having two or more amino groups and / or imino groups is particularly preferable, and ethylenediamine, hydrazine, piperazine, isophoronediamine, norbornanediamine, diethylenetriamine, and iminobispropylamine are particularly preferably used. it can.
[0019]
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 arapinogalactan, pectin, agar , Carrageenan, fercelan, alginic acid or salt thereof, proteins such as wheat protein, soybean protein, corn protein, potato protein, water-soluble organic polymer obtained from plants such as microcrystalline cellulose, corn hemicellulose, mannan, xanthan gum, Water-soluble organic polymers obtained from microorganisms such as dulan gum, curdlan, dextran, levan, cyclodextrin, pullulan, water-soluble substances obtained from animal bodies such as glue, gelatin, casein, milk protein, albumin, collagen Organic polymer, alkyl cellulose, hydroxyl alkyl cellulose, alkyl hydroxyalkyl cellulose, carboxyalkyl cellulose, carboxyhydroxyalkyl cellulose, sulfated cellulose, cellulose phosphate, carboxymethyl starch, dialdehyde starch, starch hydrogenated product, polydextrose, polyvinyl Examples include semi-synthetic and synthetic water-soluble organic polymers such as pyrrolidone, polyvinyl alkyl ether, polyacrylic acid, polymethacrylic acid and salts thereof, polyacrylamide, and propylene glycol alginate. Among these, methyl cellulose, ethyl cellulose, hydroxyl ethyl cellulose, hydroxyl propyl cellulose, carboxymethyl cellulose, sodium alginate, sodium polyacrylate and starch can be preferably used, and hydroxyl ethyl cellulose, carboxymethyl cellulose and sodium alginate are particularly preferably used. be able to. (D) By using a water-soluble organic polymer, it is possible to increase water absorption retention and (A) to promote gelation of an aqueous polyurethane liquid.
[0020]
In the method of the present invention, (A) aqueous polyurethane liquid and (B) urethane prepolymer-terminated isocyanate block product have a weight ratio in terms of solid content of both (A) :( B) = 100: 500 to 100: 1. Preferably there is. When the weight ratio in terms of solid content is less than (A) :( B) = 100: 500, (B) many active isocyanate groups are regenerated after deblocking of the urethane prepolymer-terminated isocyanate block, and it is fixed to the substrate. The cross-linking density of the resin becomes high, the texture of the flooring material for the artificial leather with silver becomes coarse and hard, the texture of the resulting artificial leather with silver becomes coarse and the bending resistance may be further lowered. When the weight ratio in terms of solid content exceeds (A) :( B) = 100: 1, (B) few active isocyanate groups are regenerated after deblocking of the urethane prepolymer-terminated isocyanate block, and it is fixed to the substrate. There is a possibility that the crosslink density of the resin is lowered, the strength of the flooring material for artificial leather with silver is lowered, and the peel strength between the flooring material and the skin layer is lowered. In the method of the present invention, the strength of the flooring for artificial leather with silver can be improved by using (A) an aqueous polyurethane liquid and (B) a urethane prepolymer-terminated isocyanate block.
[0021]
In the method of the present invention, the equivalent ratio of (B) the isocyanate group regenerated from the urethane prepolymer-terminated isocyanate block and the sum of the amino group, imino group and nitrilo group of the (C) polyamine compound is 100: 300 to 100: 30 is preferable. If the equivalent ratio of isocyanate group to 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 becomes rough, so that the resulting silver The texture of the artificial leather with attachment 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 is lowered and the strength of the flooring is lowered. There is a possibility that the peel strength of the resin may decrease. The (C) polyamine compound reacts with the isocyanate group regenerated by deblocking the (B) urethane prepolymer-terminated isocyanate blocked product to form a strong crosslink and improve the strength of the flooring.
In the method of the present invention, the weight ratio of (A) polyurethane aqueous liquid and (D) water-soluble organic polymer in terms of solid content is (A) :( D) = 100: 100 to 100: 2.5. Is preferred. If the weight ratio in terms of solid content is less than (A) :( D) = 100: 100, the viscosity of the mixed liquid used for the production of the flooring material is increased, which may make it difficult to perform the impregnation stably. There is. If the weight ratio in terms of solid content exceeds (A) :( D) = 100: 2.5, the uniformity of the resin fixed to the substrate becomes insufficient and the strength becomes weak, and the flooring and the skin layer There is a risk that the peel strength of the resin may decrease. (D) By using a water-soluble organic polymer, migration of (A) polyurethane aqueous liquid generated during drying is prevented, the uniformity of the resin fixed to the base material is increased, and a stable strength is obtained. It is possible to improve the bending resistance of the attached artificial leather.
[0022]
In the method of the present invention, in addition to (A) an aqueous polyurethane liquid and (B) a urethane prepolymer-terminated isocyanate blocked product, at least one selected from the group consisting of (C) a polyamine compound and (D) a water-soluble organic polymer. After impregnating the mixed solution containing, into a substrate such as a nonwoven fabric, a woven fabric, and a knitted fabric, and drying, a floor material for artificial leather with silver is obtained. In the method of the present invention, there is no particular limitation on the method of impregnating the substrate with the above mixed solution, and for example, an immersion 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 suitably used. The concentration of the liquid mixture and the treatment conditions can be selected as appropriate, but the weight of the resin derived from the (A) aqueous polyurethane liquid and (B) urethane prepolymer-terminated isocyanate block to be fixed to the base material is 100% by weight of the base material. The amount is preferably 1 to 300 parts by weight, more preferably 3 to 200 parts by weight, and still more preferably 5 to 150 parts by weight with respect to parts. When the amount of the resin fixed is less than 3 parts by weight with respect to 100 parts by weight of the base material, the strength of the obtained flooring material is low, and the peel strength between the flooring material and the skin layer may be lowered. When the amount of the resin fixed exceeds 200 parts by weight with respect to 100 parts by weight of the base material, the texture of the artificial leather with silver obtained by roughening the texture of the flooring becomes rough, and the flex resistance may be lowered. There is.
[0023]
In the method of the present invention, after impregnating the above mixed solution, the resin is fixed to the substrate by drying. There is no particular limitation on the drying method. For example, dry heat drying using a pin tenter, etc., wet heat drying using a high tenth Peach Steamer (HTS), a high pressure steamer (HPS), far infrared rays, and the like. Examples thereof include drying and microwave drying. Among these, wet heat drying using a high-temperture steamer, a high pressure steamer, or the like can be suitably used because the texture of the resulting flooring material is good 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, a polyimide resin, a polyamino resin, a polyacrylic resin, a polyvinyl acetate resin, ethylene / Synthetic resin dispersions such as vinyl acetate resin, polyvinyl chloride resin, epoxy resin, polyester resin, and latex dispersions such as NBR, SBR, EPR, polybutadiene rubber, butyl rubber, and natural rubber can be mixed. .
In the method of the present invention, the flooring material for artificial leather with silver can be colored as necessary. The coloring method is not particularly limited, and examples thereof include a coloring method such as a method in which a pigment is introduced into a mixed solution and impregnation, a post-dying method in which dyeing is performed after impregnation, and a pre-dying method in which dyeing is performed before impregnation. From the viewpoint of fastness of the obtained flooring material for artificial leather with silver and processing cost, an aqueous pigment is preferably used as the pigment.
[0024]
The artificial leather with silver of the present invention can be obtained by laminating or coating the skin layer on the floor material for artificial leather with silver produced by the method of the present invention. The material of the skin layer is not particularly limited. For example, polyurethane resin, polyamide resin, polyimide resin, polyamino resin, polyacrylic resin, polyvinyl acetate resin, ethylene / vinyl acetate resin, polyvinyl chloride resin Further, it can be formed using a synthetic resin such as an epoxy resin or a polyester resin, or a latex such as NBR, SBR, EPR, polybutadiene rubber, butyl rubber, or natural rubber. Of these, polyurethane resins are preferred because the texture of the resulting artificial leather with silver is flexible. There is no particular limitation on the method of forming the skin layer, and either an aqueous resin using water as a solvent or a solvent-based resin using a solvent as a solvent can be used. However, from the viewpoint of working environment and environmental problems, an aqueous resin is used. Is preferably used.
As the aqueous polyurethane resin, a polyurethane aqueous liquid similar to the forced emulsification type or self-emulsification type polyurethane aqueous liquid used as the (A) polyurethane aqueous liquid can be used. Among these, the self-emulsifying polyurethane aqueous liquid can be suitably used because the film formability 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. Moreover, various surfactants, such as a fluorine type and an acetylene glycol type, can be added as a leveling agent, and N-methylpyrrolidone, propylene glycol monomethyl ether acetate, etc. can be added as a solvent. Furthermore, if necessary, colorants such as fillers, softeners, anti-aging agents, stabilizers, adhesion promoters, antifoaming agents, and pigments can be used in combination.
[0025]
In the present invention, either a dry lamination method or a wet lamination method can be applied as a method for laminating a skin layer on a flooring material for artificial leather with silver. Among these, the dry lamination method can be suitably used because the resulting artificial leather with silver has a good texture. In the dry lamination method, a resin preparation for the skin layer, which has been adjusted to a viscosity of 1,000 to 15,000 mPa · s using a thickener, is released from the release paper so that the coating film thickness is 0.1 to 200 μm. It is coated on top and dried in a dryer at 40 to 180 ° C. to form a skin layer. Next, an adhesive adjusted to a viscosity of 1,000 to 15,000 mPa · s using a thickener is coated on the skin layer so that the coating film thickness is 0.1 to 200 μm. Dry in a dryer at ℃. Furthermore, this adhesive layer and the flooring material for artificial leather with silver obtained by the method of the present invention are bonded together and laminated with a nip roll at a temperature of 20 to 130 ° C. and a pressure of 0.98 to 29.4 MPa. After lamination, aging is preferably performed to stabilize the peel strength between the skin layer and the flooring material, and aging is preferably performed at a temperature of 30 to 70 ° C. for 1 to 3 days. After the aging is completed, the release paper is peeled off to obtain an artificial leather with silver.
[0026]
There is no restriction | limiting in particular in the adhesive agent used for a lamination process, For example, adhesive agents, such as an acrylic adhesive, a polyurethane adhesive, and a vinyl acetate adhesive, 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 can also be used as necessary. Among these adhesives, polyurethane adhesives are preferable from the viewpoint of the texture of the artificial leather with silver. Examples of the aqueous polyurethane adhesive include a one-component polyurethane adhesive and a two-component polyurethane adhesive composed of a water-dispersed polyisocyanate curing agent and an aqueous polyurethane main component. If necessary, these adhesives may contain various surfactants such as fluorine and acetylene glycol as leveling agents, and N-methylpyrrolidone, propylene glycol monomethyl ether acetate as solvents. If necessary, colorants such as fillers, softeners, anti-aging agents, stabilizers, adhesion promoters, antifoaming agents, and pigments can be added. The thickener for the skin layer and the adhesive can be used without particular limitation as long as it does not hinder the performance such as film-forming properties and adhesiveness.
[0027]
There is no restriction | limiting in particular in the coating method of the resin liquid preparation for surface skin layers, or an adhesive agent, For example, roll coating, gravure coating, knife coating, reverse coating, kiss coating etc. can be mentioned. There is no restriction | limiting in particular in a dryer, For example, a hot air dryer, an infrared irradiation dryer, a microwave irradiation dryer, a wet heat dryer etc. can be mentioned.
In the present invention, as a method of coating the skin layer on the artificial leather flooring with silver, either dry coating processing or wet coating processing can be applied, but from the viewpoint of processing cost, dry coating processing is applied. It can be used suitably. In the dry coating process, the resin layered preparation for the skin layer, which has been adjusted to a viscosity of 1,000 to 15,000 mPa · s using a thickener, is applied to the flooring material for artificial leather with silver, and the coating film thickness is 0. After coating so that it may become 1-200 micrometers, it is made to dry in 40-180 degreeC dryer, and artificial leather with silver is obtained. There is no restriction | limiting in particular in a coating system, For example, roll coating, gravure coating, knife coating, reverse coating, kiss coating etc. can be mentioned. Moreover, there is no restriction | limiting in particular also in a dryer, For example, a hot air dryer, an infrared irradiation dryer, a microwave irradiation dryer, a wet heat dryer etc. can be mentioned.
[0028]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In addition, Reference 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 of 25 mm in width and 150 mm in length, and a craft tape is bonded to the skin layer side using an iron at a temperature of 110 ° C. Using a tensile tester [Shimadzu Corporation, AUTOGRAPH AG-500D], the peel strength is measured by a T-type peel test using a tensile tester [Shimadzu Corporation, AUTOGRAPH AG-500D]. In the process of measuring peel strength, it is referred to as “floor material destruction” when the silver-added artificial leather floor material is destroyed, and “adhesive interface failure” when the adhesive interface is destroyed.
(2) Texture
The artificial leather with silver is evaluated by tactile sensation in five levels from first grade (crude) to fifth grade (flexible).
(3) Bending resistance test
The bending resistance of the artificial leather with silver is measured according to JIS K 6545-1994. Using a bending tester [Yasuda Seiki Seisakusho, No. 197 FLEXOMETER] as the testing machine, the state of damage that occurred on the test piece after 200,000 times bending was visually inspected to 1st grade (cut or marked crack) ) To 5 grades (no cracks are generated).
[0029]
Also, Reference examples, In the examples and comparative examples, the following drugs were used.
(1) Reference examples, Agents used in Examples and Comparative Examples
Polyurethane aqueous liquid for skin layer
Implanil DLV [Bayer, solid content 40% by weight]
Implanil DLF [Bayer Co., Ltd., solid content 40% by weight]
Adhesive component
Neocello 10A [Nikka Chemical Co., Ltd., 1-component water-based polyurethane adhesive]
Evaphanol HO-10 [Nikka Chemical Co., Ltd., waterborne polyurethane, main component of two-component adhesive]
Bihijoule 3100 [Sumitomo Bayer Urethane Co., Ltd., water-dispersed polyisocyanate, two-part adhesive curing agent]
Neo sticker N [Nikka Chemical Co., Ltd., thickener]
(2) Drugs used only in comparative examples
Solvent-based polyurethane resin for flooring for artificial leather with silver
Evaphanol ALS-30 [Nikka Chemical Co., Ltd., polyurethane resin, solid content 30% by weight]
Film forming aid for flooring for artificial leather with silver
NK Assist F-100 [Nikka Chemical Co., Ltd., solid content 100% by weight]
NK Assist F-200 [Nikka Chemical Co., Ltd., solid content 100% by weight]
Peaklon 700 [Nika Kagaku Co., Ltd., solid content: 100% by weight]
Solvent-based polyurethane resin for skin layers
Evaphanol D-5080 [Nikka Chemical Co., Ltd., solid content 30% by weight]
Two-component solvent-based adhesive
Neocello 150 [Nikka Chemical Co., Ltd., solvent-based polyurethane resin, main agent]
Coronate L [Nippon Polyurethane Co., Ltd., solvent-based isocyanate, curing agent]
The solid content is the heating residue (% by weight) after taking 5 g of a sample in a petri dish and leaving it in a dryer at 105 ° C. [Tabaie Speck Co., Ltd., Perfect Oven PV-210] for 3 hours.
[0030]
Production Example 1 (Production of aqueous polyurethane liquid)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 76.1 parts by weight of polytetramethylene glycol (average molecular weight 1,000), polyoxyethyleneoxypropylene random copolymer glycol ( (Average molecular weight 1,000, oxyethylene group content 70% by weight) 16.9 parts by weight, 1.5 parts by weight of 1,4-butanediol, 1.9 parts by weight of trimethylolpropane, 0.001 part by weight of dibutyltin dilaurate And 60 parts by weight of methyl ethyl ketone were added and mixed uniformly. Then, 40.4 parts by weight of dicyclohexylmethane diisocyanate was added and reacted at 75 ° C. for 300 minutes to give a urethane having a free isocyanate group content of 2.1% by weight based on the solid content. A methyl ethyl ketone solution of the prepolymer was obtained.
After cooling this solution to 30 ° C. or less, 0.1 part by weight of decyl phosphate and 6.0 parts by weight of polyoxyethylene tristyryl phenyl ether (HLB = 15) are added and mixed uniformly. Using a disper blade, 254 parts by weight of water was gradually added to phase-invert and emulsify and disperse, to which 2.0 parts by weight of piperazine and 0.8 parts by weight of diethylenetriamine were dissolved in 11.3 parts by weight of water. The solution was added and stirred for 90 minutes to obtain a polyurethane dispersion. The obtained polyurethane dispersion was further desolvated at 50 ° C. under reduced pressure to obtain a solid content of 35.2 wt%, a viscosity of 45 mPa · s (BM viscometer, No. 1 rotor, 30 rpm.), Average particle A stable aqueous polyurethane liquid having a diameter of 0.34 μm was obtained. This polyurethane aqueous liquid is designated as polyurethane aqueous liquid A1.
Production Example 2 (Production of aqueous polyurethane liquid)
In the same reactor as in Production Example 1, 60.0 parts by weight of polytetramethylene glycol (average molecular weight 1,000), 1.4 parts by weight of 1,4-butanediol, 6.6 of 2,2-dimethylolbutanoic acid 1 part by weight, 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 were mixed and mixed uniformly. Then, 40.0 parts by weight of dicyclohexylmethane diisocyanate was added, and 85 ° C. For 250 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer having a free isocyanate group content of 2.6% by weight based on the solid content.
The solution was cooled to 30 ° C. and neutralized by adding 2.5 parts by weight of triethylamine, and then 180.0 parts by weight of water was gradually added and emulsified and dispersed. To this emulsified dispersion, a polyamine solution having 2.7 parts by weight of piperazine dissolved in 20.0 parts by weight of water was added and stirred for 90 minutes to obtain a polyurethane dispersion. The obtained polyurethane dispersion was further desolvated at 50 ° C. under reduced pressure to obtain a solid content of 35.5% by weight, a viscosity of 60 mPa · s (BM viscometer, No. 1 rotor, 30 rpm), average particle diameter. A stable aqueous polyurethane liquid of 0.12 μm was obtained. This polyurethane aqueous liquid is designated as polyurethane aqueous liquid A2.
Production Example 3 (Production of urethane prepolymer-terminated isocyanate block product)
In the same reactor as in Production Example 1, 132.7 parts by weight of polyoxyethyleneoxypropylene random copolymer glycol (average molecular weight 2,200, oxyethylene group content 50% by weight), propylene oxide adduct of glycerin (average molecular weight) 1,500) 27.1 parts by weight, and after mixing uniformly, 40.2 parts by weight of isophorone diisocyanate is added and reacted at 120 ° C. for 360 minutes to give a urethane prepolymer having a free isocyanate group content of 4.0% by weight. A polymer was obtained.
The urethane prepolymer is cooled to 30 ° C., 85.0 parts by weight of isopropyl alcohol is added and mixed uniformly, and an aqueous solution in which 35.5 parts by weight of anhydrous sodium bisulfite is previously dissolved in 66.7 parts by weight of water is gradually added. In addition, 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 terminal isocyanate block dispersion. The obtained urethane prepolymer-terminated isocyanate block dispersion was a stable dispersion having a solid content of 30.0% by weight and a viscosity of 40 mPa · s (BM viscometer, No. 1 rotor, 30 rpm). This urethane prepolymer terminal isocyanate block dispersion is referred to as terminal isocyanate block dispersion B.
[0031]
Preparation Example 1 (Skin Layer Film for Laminating Process)
A polyurethane preparation for the skin layer having a composition shown below and a viscosity of 3,000 mPa · s (B-type viscometer, No. 4, rotor, 60 rpm) was prepared. After coating this on release paper [Asahi Roll Co., Ltd., Asahi Release AR-148] with a slit thickness of 150 μm (liquid material), it was dried in a hot air dryer controlled to 100 ° C. for 3 minutes and released. A skin layer film was formed on the pattern paper.
Composition of polyurethane preparation for skin layer
Implanil DLV 70.0 parts by weight
Implanil DLF 30.0 parts by weight
Neo sticker N [Nikka Chemical Co., Ltd., thickener] 3.0 parts by weight
Foam Rex 460 [Nikka Chemical Co., Ltd., antifoaming agent] 0.5 parts by weight
Sandye Super White [Sanyo Color Co., Ltd., aqueous pigment] 15.0 parts by weight
Comparative Preparation Example 1 (Skin Layer Film for Laminating Process)
A polyurethane preparation for the skin layer having a composition shown below and a viscosity of 3,000 mPa · s (B-type viscometer, No. 4, rotor, 60 rpm) was prepared. After coating this on release paper [Asahi Roll Co., Ltd., Asahi Release AR-148] with a slit thickness of 150 μm (liquid material), it was dried in a hot air dryer controlled to 100 ° C. for 3 minutes and released. A skin layer film was formed on the pattern paper.
Composition of polyurethane preparation for skin layer
Evaphanol D-5080 100.0 parts by weight
Colortex White K102 [Sanyo Color Co., Ltd., Pigment] 15.0 parts by weight
Preparation Example 2 (Skin layer polyurethane preparation for coating processing)
Each component was mixed with the composition shown below, and the liquid preparation with a viscosity of 7,000 mPa · s (B-type viscometer, No. 4, rotor, 60 rpm) was obtained.
Composition of skin layer polyurethane preparation
Implanil DLV 70.0 parts by weight
Implanil DLF 30.0 parts by weight
Neo sticker N [Nikka Chemical Co., Ltd., thickener] 6.0 parts by weight
Foam Rex 460 [Nikka Chemical Co., Ltd., antifoaming agent] 0.5 parts by weight
Sandye Super White [Sanyo Color Co., Ltd., aqueous pigment] 15.0 parts by weight
Comparative Preparation Example 2 (Skin layer polyurethane preparation for coating processing)
Each component was mixed with the composition shown below, and the liquid preparation with a viscosity of 8,000 mPa · s (B-type viscometer, No. 4, rotor, 60 rpm) was obtained.
Composition of skin layer polyurethane preparation
Evaphanol D-5080 100.0 parts by weight
Colortex White K102 [Sanyo Color Co., Ltd., Pigment] 15.0 parts by weight
[0032]
reference Example 1 (Production of artificial leather flooring with silver)
Fiber thickness 1.0 denier, density 0.40 g / cm ^Three A treatment liquid prepared by mixing 300 parts by weight of the polyurethane aqueous liquid A1, 150 parts by weight of the terminal isocyanate block dispersion B, 20 parts by weight of piperazine hexahydrate and 530 parts by weight of water in the polyester nonwoven fabric of The pad was treated with 200% by weight of pickup. After the treatment, wet-heat drying was performed for 5 minutes with a high tenpulcher steamer adjusted to a temperature of 100 ° C. and a vapor partial pressure of 39 kPa. Next, the hot water bath adjusted to 60 ° C. was washed with hot water for 10 minutes, squeezed with a mangle, and then dried with a pin tenter adjusted to 120 ° C. to obtain a flooring material for artificial leather with silver.
reference Example 2 (production of artificial leather flooring with silver)
300 parts by weight of polyurethane aqueous liquid A1, 150 parts by weight of terminal isocyanate block dispersion B, 20 parts by weight of hydroxyethyl cellulose [Daicel Chemical Industries, Ltd., HEC Daicel EP500] and 530 parts by weight of water were mixed to prepare a mixture. Except using the treated liquid reference In the same manner as in Example 1, a flooring material for artificial leather with silver was obtained.
Example 3 (Manufacture of flooring material for artificial leather with silver)
300 parts by weight of polyurethane aqueous liquid A1, 150 parts by weight of terminal isocyanate block dispersion B, 20 parts by weight of piperazine hexahydrate, 20 parts by weight of carboxymethyl cellulose [Nikka Chemical Co., Ltd., Nikka Gum C-66R] And a treatment liquid prepared by mixing 510 parts by weight of water and water, reference In the same manner as in Example 1, a flooring material for artificial leather with silver was obtained.
Example 4 (Manufacture of artificial leather flooring with silver)
340 parts by weight of aqueous polyurethane liquid A2, 150 parts by weight of terminal isocyanate block dispersion B, 20 parts by weight of piperazine hexahydrate, 20 parts by weight of carboxymethyl cellulose [Nikka Chemical Co., Ltd., Nikka Gum C-66R] And a processing solution prepared by mixing 470 parts by weight of water, reference In the same manner as in Example 1, a flooring material for artificial leather with silver was obtained.
Example 5 (Manufacture of artificial leather flooring with silver)
300 parts by weight of polyurethane aqueous liquid A1, 150 parts by weight of terminal isocyanate block dispersion B, 20 parts by weight of piperazine hexahydrate, 20 parts by weight of sodium alginate [Fuji Chemical Industry Co., Ltd., Snow Algin M] Except that the treatment liquid prepared by mixing 510 parts by weight of water was pad-treated with 100% by weight of the pickup, reference In the same manner as in Example 1, a flooring material for artificial leather with silver was obtained.
Example 6 (production of flooring material for artificial leather with silver)
Fiber thickness 1.0 denier, density 0.40 g / cm ^Three 300 parts by weight of aqueous polyurethane liquid A1, 150 parts by weight of terminal isocyanate block dispersion B, 6 parts by weight of ethylenediamine, 20 parts by weight of starch [Nikka Chemical Co., Ltd., Nikka gum 3A] and water A processing solution prepared by mixing 524 parts by weight of the mixture was pad-treated with a pickup of 200% by weight. After the treatment, it was dried by dry heat with a pin tenter adjusted to a temperature of 110 ° C. for 3 minutes. Next, the hot water bath adjusted to 60 ° C. was washed with hot water for 10 minutes, squeezed with a mangle, and then dried with a pin tenter adjusted to 120 ° C. to obtain a flooring material for artificial leather with silver.
Example 7 (Manufacture of flooring for artificial leather with silver)
100 parts by weight of polyurethane aqueous liquid A1, 420 parts by weight of terminal isocyanate block dispersion B, 16.5 parts by weight of ethylenediamine, 20 parts by weight of sodium polyacrylate [Sanyo Chemical Industries, Cellopol PC-300] And a treatment liquid prepared by mixing 443.5 parts by weight of water and water, reference In the same manner as in Example 1, a flooring material for artificial leather with silver was obtained.
Note that the above reference In the treatment liquids of Example 1 and Examples 3 to 5, the equivalent ratio of the isocyanate group derived from the blocked product of the terminal isocyanate block dispersion B and the imino group derived from piperazine hexahydrate is 100: 172. Moreover, in the process liquid of Examples 6-7, the equivalent ratio of the isocyanate group derived from the block thing of terminal isocyanate block thing dispersion liquid B and the amino group derived from ethylenediamine is 100: 172.
[0033]
Comparative Example 1 (Manufacture of flooring material for artificial leather with silver)
Fiber thickness 1.0 denier, density 0.40 g / cm ^Three Except for using a processing liquid prepared by mixing 420 parts by weight of the polyurethane aqueous liquid A1, 10 parts by weight of Neo sticker N as a migration inhibitor and 570 parts by weight of water, in the polyester nonwoven fabric. reference In the same manner as in Example 1, a flooring material for artificial leather with silver was obtained.
Comparative Example 2 (Manufacture of flooring for artificial leather with silver)
Except for using a treatment liquid prepared by mixing 470 parts by weight of polyurethane aqueous liquid A2, 10 parts by weight of Neosticker N as a migration inhibitor and 520 parts by weight of water, reference In the same manner as in Example 1, a flooring material for artificial leather with silver was obtained.
Comparative Example 3 (Production of artificial leather flooring with silver)
In the same manner as in Example 6, except that a processing liquid prepared by mixing 420 parts by weight of the polyurethane aqueous liquid A1, 10 parts by weight of Neosticker N as a migration inhibitor and 570 parts by weight of water was used, A flooring for artificial leather was obtained.
Comparative Example 4 (production of artificial leather flooring with silver)
Fiber thickness 1.0 denier, density 0.40 g / cm ^Three 500 parts by weight of Evaphanol ALS-30, 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, and 50 parts by weight of Peaklon 700 A processing solution prepared by mixing 10 parts by weight of the part and Neo sticker N was subjected to pad treatment with 230% by weight of the pickup. After the treatment, the mixture was water-coagulated for 10 minutes in a water tank adjusted to 25 ° C., and then washed with hot water in a warm water tank adjusted to 80 ° C. for 20 minutes. Next, after squeezing with a mangle, it was dried by dry heat with a pin tenter adjusted to 120 ° C. to obtain a flooring material for artificial leather with silver impregnated with solvent-based polyurethane.
Reference Examples 1 and 2 and Example 3 Table 1 shows the composition of the treatment liquid used in -7 and Comparative Examples 1-4.
[0034]
[Table 1]

[0035]
[Table 2]

[0036]
[Table 3]

[0037]
reference Example 8 (Manufacture of artificial leather with silver by laminating)
Evaphanol HO-10 (100 parts by weight), Bihijoule 3100 (7 parts by weight) and Neo-Sticker N (2 parts by weight) are mixed, and the viscosity is 3,500 mPa · s (B-type viscometer, No. 4, rotor, 60 rpm). A system adhesive 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 controlled at 100 ° C., and immediately, reference Lamination with the silver artificial leather floor material obtained in Example 1 was performed. Immediately after laminating, it was thermocompression-bonded through a nip roll adjusted to a temperature of 90 ° C. and a pressure of 1.96 MPa, and then 2 in a constant temperature and humidity chamber adjusted to a temperature of 30 ° C. and a humidity of 40% RH. Day Aged between. After aging, the release paper was peeled off to obtain an artificial leather with silver.
The performance was evaluated about the obtained artificial leather with silver. In the process of measuring the peel strength, destruction of the flooring material for artificial leather with silver was observed, making measurement impossible, and the peel strength at that time was 100 N / 25 mm. Moreover, the texture was grade 4 and the flex resistance was grade 5.
Reference Example 9 and Example 10 -14 and Comparative Examples 5-7 (production of artificial leather with silver by laminating)
reference Instead of the artificial leather flooring with silver obtained in Example 1, Reference Example 2 and Example 3 Except for using the flooring for artificial leather with silver obtained in -7 and Comparative Examples 1-3, reference In the same manner as in Example 8, an artificial leather with silver was obtained. The performance was evaluated about the obtained artificial leather with silver.
[0038]
reference Example 15 (Manufacture of artificial leather with silver by laminating)
100 parts by weight of Neocello 10A and 2 parts by weight of Neo Sticker N were mixed to prepare a one-component aqueous polyurethane adhesive having a viscosity of 2500 mPa · s (B-type viscometer, No. 4 rotor, 60 rpm).
This adhesive was coated on the skin layer side of the skin layer film obtained in Preparation Example 1 with a slit thickness of 150 μm (liquid material) and dried for 2 minutes in a hot air dryer controlled to 100 ° C., right away, reference Lamination with the silver artificial leather floor material obtained in Example 1 was performed. Immediately after lamination, the film was thermocompression bonded through a nip roll adjusted to a temperature of 90 ° C. and a pressure of 1.96 MPa, and then aged for 2 days in a constant temperature and humidity chamber adjusted to a temperature of 30 ° C. and a humidity of 40% RH. After aging, the release paper was peeled off to obtain an artificial leather with silver.
The performance was evaluated about the obtained artificial leather with silver. In the process of measuring peel strength, destruction of the flooring material for artificial leather with silver was observed, making measurement impossible, and the peel strength at that time was 87 N / 25 mm. Moreover, the texture was grade 4 and the flex resistance was grade 5.
Reference Example 16 and Example 17 -21 and Comparative Examples 8-10 (Manufacture of artificial leather with silver by laminating)
reference Instead of the artificial leather flooring with silver obtained in Example 1, Reference Example 2 and Example 3 Except for using the flooring material for artificial leather with silver obtained in ~ 7 or Comparative Examples 1-3, reference In the same manner as in Example 15, an artificial leather with silver was obtained. The performance was evaluated about the obtained artificial leather with silver.
Comparative Example 11 (Manufacture 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, and a two-component solvent-based polyurethane adhesive having a viscosity of 5,000 mPa · s (B-type viscometer, No. 4 rotor, 60 rpm) was prepared.
This adhesive was coated on the skin layer side of the skin layer film obtained in Comparative Preparation Example 1 with a slit thickness of 150 μm (liquid material) and dried for 2 minutes in a hot air dryer controlled to 100 ° C. Immediately, the laminate with the flooring for artificial leather with silver obtained in Comparative Example 4 was performed. Immediately after lamination, the film was thermocompression bonded through a nip roll adjusted to a temperature of 90 ° C. and a pressure of 1.96 MPa, and then aged for 2 days in a constant temperature and humidity chamber adjusted to a temperature of 30 ° C. and a humidity of 40% RH. After aging, the release paper was peeled off to obtain an artificial leather with silver.
The performance was evaluated about the obtained artificial leather with silver. In the process of measuring peel strength, destruction of the flooring material for artificial leather with silver was observed, making measurement impossible, and the peel strength at that time was 85 N / 25 mm. Moreover, both the texture and the bending resistance were grade 5.
Reference Examples 8 and 9, Examples 10 to 14, Reference Examples 15 and 16, Example 17 The results of -21 and Comparative Examples 5-11 are shown in Table 2.
[0039]
[Table 4]

[0040]
[Table 5]

[0041]
As seen in Table 2, in addition to the (A) aqueous polyurethane liquid and (B) urethane prepolymer-terminated isocyanate block product of the present invention, (C) a polyamine compound and / or (D) a water-soluble organic polymer Manufactured using Reference Examples 1 and 2 and Example 3 Based on the flooring of ~ 7, artificial leather with silver obtained by dry lamination, Reference Examples 8 and 9 and Example 10 Even if a two-component water-based polyurethane adhesive is used as in -14, Reference Examples 15 and 16 and Example 17 Even when a one-component water-based polyurethane adhesive is used as in -21, the floor is produced with a solvent-based polyurethane resin that has a peel strength that is high enough to cause destruction of the flooring material, is excellent in texture and flexibility. It turns out that it has a performance comparable with the flooring material for artificial leather with silver of the comparative example 11 obtained from a material and a skin layer film.
On the other hand, (A) artificial leather with silver obtained by dry lamination based on the flooring materials of Comparative Examples 1 to 3 manufactured using only an aqueous polyurethane liquid and a thickener is Comparative Examples 5 to 5. When a two-component water-based polyurethane adhesive is used as in No. 7, the peel strength is high enough to cause a flooring failure, but the texture and flexibility are inferior. When a polyurethane adhesive is used, the adhesive and the flooring are peeled off due to interfacial destruction, the adhesive strength is small, and the texture and flex resistance are also inferior.
[0042]
reference Example 22 (Manufacture of artificial leather with silver by coating)
The skin layer polyurethane preparation obtained in Preparation Example 2, reference The artificial leather with silver was coated on the artificial leather floor with silver obtained in Example 1 with a slit thickness of 200 μm (liquid) and dried for 2 minutes in a hot air dryer controlled at 100 ° C. Obtained.
The performance was evaluated about the obtained artificial leather with silver. In the process of measuring the peel strength, the floor material for artificial leather with silver was broken, and measurement was impossible. The peel strength at that time was 98 N / 25 mm. Moreover, the texture was grade 4 and the flex resistance was grade 5.
Reference Example 23 and Example 24 -28 and Comparative Examples 12-14 (Manufacture of artificial leather with silver by coating)
reference Instead of the artificial leather flooring with silver obtained in Example 1, Reference Example 2 and Example 3 Except for using the flooring material for artificial leather with silver obtained in ~ 7 or Comparative Examples 1-3, reference In the same manner as in Example 22, an artificial leather with silver was obtained. The performance was evaluated about the obtained artificial leather with silver.
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. reference Except for using the artificial leather flooring with silver obtained in Comparative Example 4 instead of the artificial leather flooring with silver obtained in Example 1, reference In the same manner as in Example 22, an artificial leather with silver made of a conventional solvent-based polyurethane resin was obtained. The performance was evaluated about the obtained artificial leather with silver.
Reference Examples 22 and 23 and Example 24 Table 3 shows the results of -28 and Comparative Examples 12-15.
[0043]
[Table 6]

[0044]
As seen in Table 3, in addition to the (A) polyurethane aqueous liquid and (B) urethane prepolymer-terminated isocyanate block product of the present invention, (C) a polyamine compound and / or (D) a water-soluble organic polymer Manufactured using Reference Examples 1 and 2 and Example 3 The artificial leather with silver obtained by coating processing based on the flooring material of ~ 7 has a peel strength that is high enough to cause the flooring material to break, is excellent in texture and flexibility, and is a conventional solvent-based polyurethane resin. It can be seen that it has the same performance as the artificial leather with silver of Comparative Example 15 obtained from
On the other hand, (A) artificial leather with silver of Comparative Examples 12 to 14 based on a flooring produced using only an aqueous polyurethane liquid and a thickener has a peel strength enough to cause flooring destruction. However, the peel strength compared to the artificial leather with silver of the present invention is slightly smaller, and the texture and the bending resistance are inferior.
[0045]
【The invention's effect】
When using the flooring material for artificial leather with silver produced by the method of the present invention, the peel strength, texture, and bending resistance can be obtained even with the use of a water-based polyurethane resin skin layer or adhesive that has been problematic in terms of performance. The artificial leather with silver excellent in property can be obtained. The artificial leather with silver of the present invention is inferior to the artificial leather with silver obtained from a conventional solvent-based polyurethane resin, and it is not necessary to use a solvent substantially and can be replaced with 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, the labor of collecting the solvent, and the worker's working environment.

Claims (7)

  (A) In addition to (A) polyurethane aqueous liquid and (B) urethane prepolymer terminal isocyanate blocked product, (C) a liquid mixture containing a polyamine compound and (D) a water-soluble organic polymer is impregnated into a substrate, and then dried. A method for producing a flooring material for artificial leather with silver, characterized in that:   (A) An aqueous polyurethane solution is obtained by emulsifying and dispersing an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate and a polyol with water using a nonionic surfactant of HLB7-16, Alternatively, the method for producing a flooring material for artificial leather with silver according to claim 1, wherein the floor material is obtained by chain elongation reaction with a polyamine compound having two or more imino groups.   (A) A polyurethane aqueous liquid is obtained by emulsifying and dispersing, in water, 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. 2. The method for producing a flooring material for artificial leather with silver according to claim 1, which is obtained by a chain elongation reaction using a polyamine compound having two or more amino groups and / or imino groups.   (B) The method for producing a flooring material for artificial leather with silver according to claim 1, wherein the urethane prepolymer terminal isocyanate block product is a terminal isocyanate block product of bisulfite.   (C) The method for producing a floor covering for artificial leather with silver according to claim 1, wherein the polyamine compound is a compound having two or more amino groups and / or imino groups.   (D) The water-soluble organic polymer is at least one polymer selected from the group consisting of methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, sodium alginate, sodium polyacrylate, and starch. The manufacturing method of the flooring for artificial leather with description of description.   An artificial leather with silver, which is obtained by laminating or coating an outer skin layer on a floor material for artificial leather with silver obtained by the production method according to any one of claims 1 to 6.