JP3145521B2 - Synthetic leather surface treatment finishing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing synthetic leather having a gloss of 50 or less and improved dye transferability, and a dyed synthetic leather.

[0002]

2. Description of the Related Art Conventionally, dyeing of synthetic leather and artificial leather with a dye has been performed (JP-A-63-30967).
7, JP-A-2-251682). There is also known a method of dyeing by introducing synthetic leather into an organic solvent solution of a disperse dye insoluble in water (JP-A-63-59487). Further, a method of coloring synthetic leather with a solution system in which the solubility of a disperse dye is improved is also known from JP-A-3-76878. In order to dye synthetic leather with a disperse dye that does not substantially dissolve in water, a method of once dissolving the disperse dye in an organic solvent to prepare a dye bath, and introducing the synthetic leather into the dye bath to dye the synthetic leather. Can be Japanese Patent Laid-Open No. Hei 3
In JP-76878-A, a ketone-based solvent such as acetone and methyl ethyl ketone, and a dioxane solvent are used as solvents in order to improve the solubility of a disperse dye and to penetrate and dye the dye in a synthetic leather resin layer. The publication also discloses a method of improving the easy dyeing effect by adding a solvent such as polyoxyethylene glycol which promotes the solubility of a disperse dye to an organic solvent. In the step of coloring the synthetic leather, in order to smoothly perform the coating operation of the dye contained therein, the solvent containing the dye for dyeing the synthetic leather improves the solubility of the dye, but the urethane resin constituting the synthetic leather Should not dissolve,
It has been shown that a solvent having a high boiling point such as ethylene glycol or propylene glycol can be used as a solvent having such desirable properties (Japanese Patent Laid-Open Publication No. Hei 3-
76878). Further, it is disclosed that cyclohexanone, methylcellosolve, methylcellosolve acetate, dimethylformamide and the like are used as solvents depending on the properties of the dye (promoting the solubility of the dye). On the other hand, mere dyeing with a disperse dye has the disadvantage that the dye migrates to the surface of synthetic leather. Conventionally, therefore, special measures have been taken to introduce a nitrogen atom-containing functional group into a resin component constituting synthetic leather (Japanese Patent Laid-Open No. 55-408).
No. 33). In such a conventional method of dyeing synthetic leather with a dye, a method in which a resin component constituting the synthetic leather is provided with a special functional group is used. However, when the synthetic leather is dyed by the dyeing method of these conventional methods, a problem that the dye is easily transferred from the dyed synthetic leather easily occurs. It is necessary to introduce a functional group. Therefore, the production process of the urethane resin for synthetic leather becomes complicated and expensive. In the case of dyeing using a disperse dye that does not dissolve in water, it is necessary to use a dye bath in which the dye is dissolved in an organic solvent or a coating solution. In this case, in the solvent used in the prior art, the urethane resin is partially dissolved when penetrated into the synthetic leather raw material as a dye medium, so that the dyed synthetic leather is glossier than the raw material. This causes the appearance of the product to deteriorate, and a matte product having a calm feeling cannot be obtained. Furthermore, when the surface layer of the synthetic leather is manufactured by a release paper transfer method,
The colored luster and squeeze transferred from the release paper are dissolved by the solvent of the dye. Therefore, these prior arts focus only on the mere coloring of synthetic leather, which significantly impairs the characteristics of gloss adjustment and squeezing, which are important features required for synthetic leather. That is, in the conventional dyeing technique, when the raw material is coated, coated, and dipped using a solvent other than water, in any case, the raw material is in a glossy state. Therefore, in the conventional method of dyeing or coating a raw material, if it is desired to obtain a matte surface state at the same time as dyeing, a coating liquid containing a matting agent such as colloidal silica or polyethylene wax in a treatment liquid such as a paint in advance. Must be used. When a coating solution containing such a matting agent is used, the matting state is caused by irregular reflection of the matting agent fine powder dispersed on the surface of the synthetic leather, and therefore, there is a disadvantage that scratch resistance due to physical friction is reduced. . In particular, when the glossiness at 60 degrees is 5 to 20, the scratch resistance is significantly reduced. Furthermore, when the raw material is immersed in a medium obtained by mixing an organic solvent such as MEK, toluene, ethyl acetate, methyl cellosolve, tetrahydrofuran, DFM, and dioxane in methanol of the prior art, the elastic polymer on the surface of the raw material partially becomes As a result, the surface state becomes smooth and glossy, and the squeezing state changes, resulting in a so-called squeezing flow state. Furthermore, when the elastic polymer on the surface of the raw material is porous, the porous structure is partially destroyed by dissolution, and the characteristics of the raw material are lost.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a method for dyeing synthetic leather having an improved transfer resistance of dyeing, a less glossy finish, and a synthetic leather dyed by the dyeing method. The purpose is to do so.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a cationic resin is previously fixed inside synthetic leather as a pretreatment of the dyeing step in order to suppress the transfer of dyeing of synthetic leather. By adsorbing the dye on this, preventing the transfer of dyeing, by using a lower alcohol as a solvent,
By suppressing the dissolution of the synthetic leather material, and by allowing the water to finally evaporate after the solvent evaporates, it has been found that the gloss can be prevented from increasing by dyeing, and the object of the present invention can be achieved. Was.

That is, the present invention relates to a cationic resin bath containing 100 parts by weight of a lower alcohol having 4 or less carbon atoms, 0.01 to 10 parts by weight of a cationic resin, and 1.0 to 20 parts by weight of water. Then, 80 to 95 parts by weight of a lower alcohol having 4 or less carbon atoms, 20 to 5 parts by weight of water, 0.01 to 10 parts by weight of an oil-soluble dye, and 0.01 of a water-soluble ionic compound.
The present invention provides a method for dyeing synthetic leather, characterized by dyeing with a dye bath containing up to 0.5 parts by weight, and a synthetic leather dyed by this dyeing method. The dyeing method of the present invention can be applied to synthetic leather known in the synthetic leather industry without any particular limitation. Specifically, the present invention is applied to (1) wet synthetic leather, (2) artificial leather, (3) dry synthetic leather, (4) plasticized vinyl chloride sheet, or synthetic leather in which a urethane resin film is laminated on a sponge sheet. be able to. The base material constituting the synthetic leather is an elastic polymer, a nonwoven fabric containing a modified elastic polymer, or a base material composed of the elastic polymer itself. Of these elastic polymers and modified elastic polymers, particularly important ones are urethane resin elastic polymers, acrylic resins and polyamide resins. Further, a plasticizer vinyl chloride can also be used as a preferable base material as a synthetic leather constituent base material. The synthetic leather dyeing method of the present invention is a method of pretreating a synthetic leather raw material in a cation resin bath, and then dyeing the raw material in a dye bath. The cationic resin bath of the present invention comprises 100 parts by weight of a lower alcohol having 4 or less carbon atoms, 0.01 to 10 parts by weight of a cationic resin,
It is a cationic resin solution containing 1 to 20 parts by weight of water. The dye bath of the present invention comprises a lower alcohol having 4 or less carbon atoms of 80 to 95.
This is a liquid composition containing 20 parts by weight of water, 20 to 5 parts by weight of water, 0.01 to 10 parts by weight of an oil-soluble dye, and 0.01 to 0.5 parts by weight of a water-soluble ionic compound.

As the lower alcohol having 4 or less carbon atoms used in the cationic resin bath and the dye bath of the present invention, for example, methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol and the like can be used. Of these, methanol is particularly preferred in terms of low boiling point and solubility in synthetic leather. The cationic resin used in the cationic resin bath of the present invention is a polymer compound having a nitrogen atom serving as a cation in a molecule, for example, cationic urethane, cationic acrylic resin or commercially available Daiichi Kogyo Seiyaku Co., Ltd. Quaternary ammonium salt type cationic polymer (Shalol DM-283P, DM-663P, DM-254P)
Can be used. As the cationic urethane resin used in the cationic resin bath of the present invention, an alcohol-soluble cationic urethane resin having a terminal NH ₂ group obtained from a terminal OH group-containing polyfunctional polyol, a diisocyanate compound, and a diamine compound is used. Can be. In this urethane resin, the ratio NCO / OH between isocyanate groups and hydroxyl groups is 1.7 to 2.0, and NH ₂ /
NCO having a ratio of 2.0 to 1.2 can be suitably used.

The bifunctional polyol having a terminal OH group having a molecular weight of 1,000 to 6,000 can be used as the raw material of the cationic urethane resin used in the present invention. In particular, the following polyols are preferred. Polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide propylene oxide copolymer, polyethylene glycol polycaprolactone copolymer, polypropylene glycol polycaprolactone copolymer, polytetramethylene glycol polycaprolactone copolymer, Polyethylene glycol polyvalerolactone copolymer, polypropylene glycol polycaprolactone copolymer, polytetramethylene glycol polycaprolactone copolymer lactone polyol polycaprolactone polyol, polyvalerolactone polyol, lactone block copolymer polyol, valerolactone copolymer polyol polyester polyol Poly from diols and dibasic acids Ester polyol Diol; ethylene glycol, diethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, dimer diol, dibasic; adipic acid, sebacic acid, azelaic acid, isophthalic acid, terephthalic acid, malene, fumaric acid, dimer acid Polycarbonate diol Any of the above-mentioned mixed polyols. Further, as the diisocyanate compound used in the cationic urethane resin of the present invention, those listed below can be suitably used. Aliphatic diisocyanate compound example Hexamethylene diisocyanate, TMXDI Aliphatic diisocyanate compound such as isophorone diisocyanate, water-added xylene diisocyanate, water-added MDI aromatic diisocyanate compound such as TDI, MD
I Any of the above mixed diisocyanate compounds. As the chain extender used in the cationic urethane resin of the present invention, those listed below can be suitably used. As an aliphatic diamine compound, for example, ethylenediamine, hexamethylenediamine, etc. As an alicyclic diamine compound, for example, isophoronediamine, water-added 4,4′-diaminodiphenylmethane, etc. As an aromatic diamine compound, for example, xylenediamine, 4,4′-diamino Diphenylmethane and the like.

The cationic acrylic resin used in the present invention comprises 30 units of an amide or amino group-containing acrylic monomer.
It is possible to use a lower alcohol soluble cationic acrylic resin containing at least% by weight. Such amides,
As the amino group-containing acrylic monomer, for example, N,
N-dimethylaminoethyl acrylate, N, N-dimethylaminopropylacrylamide, N, N-dimethylacrylamide, acroylmorpholine, N-isopropylacrylamide, and the like can be used. The cationic acrylic resin used in the present invention includes these amides, amino group-containing acrylic monomers and other copolymerizable monomers such as methyl (meth) acrylate, methacrylic acid,
Hydroxyl (meth) acrylate, glycidyl (meth)
Copolymers with acrylates, styrene monomers and the like can be used. As these monomers, those synthesized by a conventional method can be used, and the obtained polymer can be used by dissolving it in an alcohol having 4 or less carbon atoms. As the oil-soluble dye used in the dye bath of the present invention, a sulfonic acid group, a water-soluble functional group such as a carboxyl group can be used without any particular limitation as long as it is a disperse dye substantially insoluble in water. Known oil-soluble dyes used in the above-mentioned methods can be used, and specific examples thereof include Aizen, Spiron (manufactured by Hodogaya Chemical), Kayaron (manufactured by Nippon Kayaku), and Miketron (manufactured by Mitsui Toatsu Chemical). Can be.
The water-soluble ionic compound used in the dye bath of the present invention can be used without particular limitation as long as it has an action of ionizing a nitrogen atom in a cationic resin into a nitrogen cation. For example, organic acids such as acetic acid, citric acid and oxalic acid, and water-soluble inorganic compounds such as hydrochloric acid and magnesium chloride can be used, and organic acid compounds are preferable. The content ratio of water to the lower alcohol having 4 or less carbon atoms in the cationic resin bath is in the range of 1 to 20 parts by weight. If the amount of water is more than 20 parts by weight, the disperse dye precipitates in the solvent, causing uneven dyeing.

In the dye bath of the present invention, water is a lower alcohol 8
5 to 20 parts by weight of water is used for 0 to 95 parts by weight. If the amount of water is less than 5 parts by weight, the luster increases, and if it exceeds 20 parts by weight, the solubility of the oil-soluble dye is reduced, and the amount of the oil-soluble dye used is limited. The saturation solubility of a general disperse dye in various solvents and a mixed solvent with water / about 20 ° C. is generally in the following situation. Solubility of oil-soluble dye trade name Spiron dye [Hodogaya Chemical Co., Ltd.] (Spiron Oren @ 2RH) Water Substantially insoluble Methanol 4.2% by weight Acetone 28.6% by weight Sacsan ethyl 5.6% by weight Methyl cellosolve 13. 2% by weight Ethylene glycol Dispersion state-Dissolution state is difficult to distinguish Propylene glycol Dispersion state-Dissolution state is difficult to distinguish Polypropylene glycol Dispersion state-Dissolution state is difficult to distinguish Mixed solvent Approx. b methanol 80 20-30% by weight acetone 20 c methanol 80 20-30% by weight methyl ethyl ketone 20 d methanol 80 6-8% by weight propylene glycol 20e methanol 80 5-7% by weight propylene glycol 20 Within the scope of the present invention Well, water As the amount is large, disappears gloss of synthetic leather, there is a tendency to gloss appears according to the amount of water is reduced. According to the dyeing method of the present invention, a dyed synthetic leather having a 60 degree gloss of 50 or less, preferably 30 or less can be obtained.

In the dyeing method of the present invention, the dissolution amount (addition weight) of the oil-soluble dye in the dye bath in the alcohol solvent is determined in consideration of the desired luster and transfer resistance, based on the above-mentioned water-alcohol mixed solvent. It is desirable to use within such a saturation concentration. Further, from the viewpoint of reducing the bleeding of the dye of the dyed synthetic leather, the smaller the dyeing amount of the dye, the better. Therefore, in the method of the present invention, after the synthetic leather is immersed in the dye bath by adjusting the addition weight of the oil-soluble dye, the dye dyeing amount is reduced to 0.2 parts by weight or less based on 100 parts by weight of the to-be- dyed body. It is desirable. In the dyeing method of the present invention, when synthetic leather is immersed in a cationic resin bath, the cationic resin in the cationic resin bath is adsorbed in the elastic polymer constituting the synthetic leather. Then, the lower alcohol and water in the cation resin bath are evaporated and dried to fix the cation resin in the synthetic leather. Normally immersion time is under normal temperature and normal pressure,
The fixation of the cationic resin is completed in about 3 to 10 minutes. Further, it is presumed that the action of water in the cationic resin bath facilitates the adsorption of the cationic resin itself to the synthetic leather resin component. By dyeing the synthetic leather fabric treated by the cationic resin bath with a dye bath, the oil-soluble dye that has penetrated into the synthetic leather fabric is converted into a cationic resin existing in the synthetic leather by the cationic resin bath. A dyed product which is fixed in a state of being aggregated by the resin and has migration resistance is obtained. It is presumed that the presence of water in the dye bath contributes to promoting the disperse dye in the lower alcohol in the tendency to form ultrafine particles and making the dye more easily adsorbed to the cationic resin. As described above, the presence of the water in the cationic resin bath and the dye bath contributes to the improvement of the adsorption capacity of the cationic resin, and plays an important role in the action mechanism of the present invention. In the dye bath, the pre-treated raw material is 3 to 10 at room temperature and pressure.
After the synthetic leather is immersed for a minute and then dried, the synthetic leather can be dyed and, at the same time, matted in glossiness from before the immersion, and the synthetic leather can be obtained. The water contained in the dye bath is evaporated and dried later than the coexisting alcohol solvent. Therefore, the surface of the synthetic leather elastic polymer becomes a finely porous state (blancheeng state) due to a slight difference in the evaporation and drying state of these media, and becomes a matte state. Thus, the water contributes to the luster control by means of the medium of cationization of the nitrogen atoms for the penetration of the cationic resin into the synthetic leather and the evaporation time with the alcohol. Further, the water-soluble ionic compound contributes to cationization of the cationic resin. The dyeing method of the present invention, synthetic leather raw fabric,
The portions to be dyed and matted by immersion in a dye bath correspond to the elastic polymer portion forming the surface of the synthetic leather raw fabric and the back surface and side surface of the base material constituting the synthetic leather raw fabric.

[0011]

【Example】

Example: Synthesis example of urethane resin for synthetic leather [A-1] Synthesis of urethane resin for wet synthetic leather porous layer 1,4-butanediol adipate (polyol component) 80.75 g (OHvＯＨ56, molecular weight about 2,000, 1,4-butanediol (chain extender) 2.42 g MDI 16.82 g dibutyltin laurate (catalyst) 0.01 g DMF (solvent) 233.00 g DMF 30 in a 1000 ml urethane resin synthesis reactor
%, And a polyol and a chain extender were heated to 60 to 70 ° C., and 90% of the MDI was added while uniformly stirring the whole.
Heat to 95 ° C. Next, after the catalyst is added, the remaining MDI is added evenly in three portions while the reaction is continued for 3 hours under these reaction conditions, and during this time, the remaining DMF is added in three portions as the viscosity increases. After all the raw materials have been added, the reaction is further continued for 1 hour under the same conditions, and then the heating is stopped, the mixture is allowed to cool, and the temperature of the contents is lowered to room temperature. The resulting urethane resin solution had a solid content of 30% and a viscosity of about 700 poise / 25 ° C. This is designated as urethane resin solution A-1.

[A-2] Synthesis of urethane urea resin for synthetic leather top skin layer. Part 1 75.60 g of caprolactone polyol (polyol component) (OHv ≒ 56, molecular weight about 2,000, bifunctional) 1,3-butanediol (Chain extender) 2.50 g Zinc octylate (catalyst) 0.005 g Hexamethylene diamine (Chain extender) 3.90 g Dibutylamine (Reaction terminator) 0.40 g Hexamethylene diisocyanate (HDI) 17.40 g Toluene (Solvent) 100.0 g Isopropyl alcohol (solvent) 50.00 g Toluene 2 in a 1000 cc urethane resin synthesis reactor
7.30 g, polyol, 1,3-butanediol, and the entire amount of the catalyst were charged, and the whole amount of HDI was added while uniformly stirring the whole, and the whole was continuously stirred and the temperature was raised to 85 to 90 ° C. over about 1 hour. Warm up. After continuing the reaction for 3 hours, the heating was stopped, 22.70 g of toluene was added, and the temperature of the content was rapidly cooled to 20 ° C. or less to produce a urethane polymer solution having a solid content of 50%. On the other hand, the remaining amount of toluene, isopropyl alcohol,
A solution obtained by uniformly mixing the total amount of hexamethylenediamine and dibutylamine is charged into a reaction vessel, and while stirring vigorously, the temperature of the content is maintained at 20 ° C. or lower, and the urethane prepolymer solution is charged, and the temperature of the content is lowered. After the temperature was raised to 40 ° C. over 1 hour, the temperature was allowed to cool, and the temperature of the content was lowered to room temperature. The resulting urethane resin solution, solid content 30%,
The viscosity was about 400 poise / 25 ° C. This is designated as urethane resin solution A-2.

[A-3] Synthesis of urethane resin for synthetic leather top skin layer, part 2 80.75 g of tetramethylene glycol (polyol component) (OHv ≒ 56, molecular weight about 2,000, bifunctional) 1,4-butanediol (Chain extender) 2.42 g dibutyltin laurate (catalyst) 0.01 g MDI 16.82 g polyol in a 1000 cc urethane resin synthesis reactor
The total amount of the chain extender and catalyst is charged, and the temperature is brought to about 80 ° C. while uniformly stirring the whole. On the other hand, the whole amount of MDI is charged into another reactor, and the MDI is brought to a melting temperature of 80 ° C. Next, the dissolved MDI is charged into a reaction vessel containing the polyol, and immediately and uniformly stirred, the contents are immediately placed in a container having releasability, and the mixture is allowed to react at a temperature of about 80 ° C. for 2 hours, and the desired urethane resin is reacted. Get. The viscosity of a tetrahydrofuran solution containing 10% of this urethane resin is 500 cps / 25.
° C. This is designated as urethane resin solution A-3.

[A-4] Synthesis of urethane resin for synthetic leather (moisture permeable) top skin layer. Part 3. 10.75 g of tetramethylene glycol (polyol component) (OHv ≒ 56, molecular weight about 2,000, bifunctional) Polyethylene glycol (Polyol component) 70.00 g (OHv ≒ 56, molecular weight about 2,000, bifunctional) 1,4-butanediol (chain extender) 2.42 g MDI 16.82 g dibutyltin laurate (catalyst) 0.01 g DMF (solvent) ) 233.00 g The synthesis method is exactly the same as in the case of [A-1] Synthesis of urethane resin for wet synthetic leather porous layer. Obtained urethane resin solution, solid content 30%, viscosity about 420 poise / 25
° C. This is designated as urethane resin solution A-4.

[A-5] Synthetic leather: synthesis of prepolymer for adhesive 1,4-butanediol adipate (polyol component) 42.50 g (OHv ≒ 36, molecular weight about 3000, bifunctional) TDI 2.50 g dibutyltin Laurate (catalyst) 0.005 g Toluene 55.00 g Toluene 30 in a 1000 cc urethane resin synthesis reactor
% And the total amount of the polyol and the chain extender are charged to 60 to 7
The mixture was heated to 0 ° C., and 90% of TDI was added thereto while uniformly stirring the whole.
Heat to ° C. Next, after the catalyst is added, the remaining TDI is added evenly in three portions while stirring is continued for 3 hours under the reaction conditions, and during this time, the remaining DMF is added in three portions as the viscosity increases. After all the raw materials were added, the reaction was continued for 1
Stop heating, let cool down, and cool the contents to room temperature. Obtained urethane resin solution, solid content 45
%, Viscosity was about 1500 poise / 25 ° C. This is designated as urethane resin solution A-5.

[A-6] Synthesis of urethane emulsion resin solution for synthetic leather top skin layer Polycarbonate diol (polyol component) 82.10 g (OHv ≒ 56, molecular weight about 2,000, bifunctional) diethylenetriamine (chain extender) 80 g Zinc octylate (catalyst) 0.005 g Dibutylamine (reaction terminator) 0.20 g Hexamethylene diisocyanate (HDI) 13.80 g Acetic acid (neutralizing agent) 1.60 g Acetone (solvent) 100.00 g Ion-exchanged water 100. Acetone 3 in a reaction vessel for urethane resin synthesis
3.30 g, the whole amount of the polyol component and the catalyst are charged, and the whole amount of HDI is added while uniformly stirring the whole, and the whole is further stirred and the temperature is raised to a temperature of 60 to 70 ° C. over about one hour. After the reaction was continued for 3 hours, the heating was stopped, and 50.70 g of ascent was added.
Cool rapidly to below ℃ to produce urethane prepolymer.
While maintaining the temperature of the content at 20 ° C. or lower, vigorous stirring is continued, and a solution of diethylenetriamine and dibutylamine dissolved in the remaining ascent is added little by little to complete the chain extension reaction, thereby obtaining an ascent solution of a 50% urethane resin. Next, while gradually adding 100 g of ion-exchanged water and 1.60 g of acetic acid to the ascent solution of the urethane resin, the whole urethane resin is emulsified in water while the whole is mechanically vigorously stirred. Let it. Thereafter, the pressure in the reactor was reduced and the ascent was removed from the system to obtain a urethane resin emulsion solution. This is designated urethane resin solution A-6.

[1] Example of urethane synthetic leather used in the present invention (1-1) Artificial leather raw fabric manufacturing method 1a) Formulation example Urethane resin solution [A-1] 100 parts by weight DMF 50 parts by weight Surfactant 2 parts by weight Part Seika Seven BS1001 white 10 parts by weight ¹⁾ Note 1) Colorant for urethane resin manufactured by Dainichi Seika Kogyo Co., Ltd. 1b) Example of production method The above 1a) The composition is applied to a non-woven fabric at about 500 g / m ^2.
Wet application, immediate introduction into water, coagulation on urethane simultaneously with removal of DMF. The residual solvent and surfactant are thoroughly washed with water and then dried to obtain the desired wet synthetic leather. 1c) The nonwoven fabric in this case is a nonwoven fabric made of a thermoplastic urethane resin having the same weight as about 1 denier polyester fiber. 1d) The wet synthetic leather fabric obtained in 1b) is 60
Degree and glossiness were 5. 1e) Hereinafter, this is referred to as a raw material [B-1]. (1-2) Synthetic leather raw material production method 2a) Example of synthetic leather surface skin layer composition Urethane resin solution A-1 100 parts by weight Cellulose acetate butyrate 1.5 parts by weight Seika Seven MU1001 white 20 parts by weight ⁴⁾ MEK 50 parts by weight Note 4) Urethane resin coloring agent manufactured by Dainichi Seika Kogyo Co., Ltd. 2b) Adhesive layer composition example Urethane resin solution A-5 100 parts by weight Resamine UD-C 8 parts by weight ⁶⁾ Seika Seven MU1001 white 5 parts by weight ⁷⁾ DMF 10 parts by weight Ethyl acetate 40 parts by weight Note 6) Curing agent for urethane resin manufactured by Dainichi Seika Kogyo Co., Ltd. 7) Colorant for urethane resin manufactured by Dainichi Seika Kogyo Co., Ltd. About 100g / m ²
・ Wet coating, immediately forming a urethane resin leather film while drying with hot air, laminating the above composition 2a), laminating a polyester woven fabric while drying with hot air at about 100 g / m ²・ wet, Further, the remaining solvent is heated and dried at a temperature of about 120 ° C. to obtain a synthetic leather raw material for winding. 2c) In this case, the release paper used has a constriction of irregularities of about 1-2 μm, and a further 60 °. The thing of glossiness 10 was used. 2b) In the synthetic leather raw material obtained in the above 2b), the squeezing was almost reproduced, and the 60 ° and glossiness were almost reproduced at 9 to 10 as well. 2e) Hereinafter, this is referred to as a raw material [B-2].

(1-3) Example of a method of producing a moisture-permeable synthetic leather raw fabric (porous) 3a) Example of blending a moisture-permeable synthetic leather and a moisture-permeable layer 100 parts by weight of Heimlen Y229 ⁸⁾ 20 parts by weight of NEK 16 parts by weight of toluene Water (ion) Exchange water) 50 parts by weight Heimlen X2093 white 2 parts by weight ⁹⁾ Note 8) Dry-type moisture-permeable synthetic leather resin solution manufactured by Dainichi Seika Kogyo Co., Ltd. 9) Colorant for urethane resin manufactured by Dainichi Seika Kogyo Co., Ltd. After mixing water and water, other raw materials are blended and the whole is uniformly mixed. About 100 g / m ² · wet is applied to this blended liquid on a polyester woven fabric and dried with hot air to obtain the desired raw material of moisture-permeable synthetic leather. The obtained web is 60
And glossiness were 8-10. 3b) Hereinafter, this is referred to as a raw material [B-3]. (1-4) Artificial leather raw material manufacturing method-24a) The manufacturing method is exactly the same as the above-mentioned raw material [B-2].
Instead of using a polyester woven fabric as the base material, the raw material [B-1] was used as the base material. 4b) A synthetic leather raw material having a constriction of approximately 1 to 2 μm and a gloss of 9 to 10 was obtained. 4c) Hereinafter, this is referred to as a raw material [B-4]. (1-5) Moisture-permeable synthetic leather raw material production method, part 25a) Compounding solution for top skin layer Urethane resin solution A-4 100 parts by weight Cellulose acetate butyrate 1.5 parts by weight Titanium oxide (pigment) white 5 parts by weight MEK 15 parts by weight The above composition 5a) is applied to the release paper surface at a rate of about 100 g / m 2.
^2. While forming a wet-coated and semi-dried urethane resin film, it is bonded to the raw material [B-3] obtained in the above 1-3) to obtain a target synthetic leather raw material. 5b) A synthetic leather raw material having a constriction of approximately 1 to 2 μm and a gloss of 9 to 10 was obtained. 5c) Hereinafter, this is referred to as a raw material [B-5].

(1-6) Vinyl chloride synthetic leather raw material production method 6a) Example of formulating topskin resin layer Urethane resin solution A-2 100 parts by weight Cellulose acetate butyrate 1.5 parts by weight Titanium oxide (pigment) white 5 parts by weight MEK 10 parts by weight IPA 5 parts by weight 6b) Adhesive layer composition example Urethane resin solution A-5 100 parts by weight ⁵⁾ Resamine UD-C 8 parts by weight ⁶⁾ Seika Seven MU1001 white 5 parts by weight ⁷⁾ Dimethylformamide 10 parts by weight acetic acid Ethyl 40 parts by weight Note 5) 6) Curing agent for urethane resin manufactured by Dainichi Seika Kogyo Co., Ltd. 7) Colorant for urethane resin manufactured by Dainichi Seika Kogyo Co., Ltd. About 100g / m
^2. Apply wet and immediately dry with hot air to form a urethane resin film, and apply the composition shown in 6b) above to about 100
A soft vinyl chloride scissor was adhered while applying hot air with g / m ² · wet to obtain artificial leather having a urethane resin film. 6b) A synthetic leather raw material having a constriction of approximately 1 to 2 μm and a gloss of 9 to 10 was obtained. 6c) This is used as a raw material [B-6]. (1-7) Artificial Leather Fabric Production Method Part 3 7a) Formulation Example of Urethane Resin Paint for Gravure Roll Coating Urethane Resin Solution A-3 100 parts by weight Seika Seven MU1001 White 1 part by weight Nitrified cotton 1 part by weight -1] Using a 100] mesh gravure roll on the surface, the urethane resin paint shown in 7a) was applied three times and dried to obtain a wet synthetic leather raw material having a surface gloss of about 70. 7b) Hereinafter, this is referred to as a raw material [B-7].

(1-8) Wet Leather Raw Material Production Method No. 48a) Example of Formulation of Urethane Resin Paint for Gravure Roll Coating 100 parts by weight of urethane resin solution A-2 1.5 parts by weight of cellulose acetate butyrate Titanium oxide (pigment) ) White 5 parts by weight MEK 200 parts by weight IPA 100 parts by weight 8 b) Formulation example of urethane resin coating for gravure roll coating Urethane resin solution A-3 100 parts by weight Seika Seven MU1001 White 1 part by weight Nitrified cotton 1 part by weight The raw material [B -1] Using a 100 Messi gravure roll on the surface, apply the urethane resin paint shown in 8a) above to 3
The urethane resin paint shown in 8b) was further applied twice and dried twice to obtain an artificial leather raw material having a surface gloss of about 70. 8c) Hereinafter, this is referred to as a raw material [B-8]. (1-9) Artificial Leather Fabric Production Method, Part 59 a) Example of Formulation of Urethane Emulsion Resin Paint for Top Skin Urethane Emulsion Resin Solution A-6 100 g Titanium White (Pigment) 2.0 g Nonionic Surfactant 1.0 g Antifoaming Agent 0.001 g Carboxymethylcellulose (thickening agent) 0.5 g Colloidal silica (anti-blocking agent) 1.0 g 9b) About 100 g of the paint shown in 9a) above was applied to the surface of the raw material [B-1] using a knife coater. -Wet / m ^{2 was} applied and dried to obtain a synthetic leather raw material having a surface glossiness of about 30. 9c) Hereinafter, this is referred to as a raw material [B-9]. Raw fabric dyeing Example: Cationic resin treatment liquid 1) Treatment liquid K-1 Charol DM-283P 5.0 g Methanol 100.5 g Water 5.0 g 2) Treatment liquid K-2 Cationic urethane resin solution 50.0 g Methanol 50 0.0g 3) Treatment solution K-3 Cationic acrylic resin solution 50.0 g Methanol 50.0 g Cationic urethane resin solution and acrylic resin solution used in 2) and 3) above were manufactured according to the following formulation. One used. Preparation example of cationic urethane resin solution Molecular weight: about 1000, PPG containing terminal OH group: 1000 g
(1.0 mol), isophorone diisocyanate; 44
4 g (2.0 mol), NCO / OH = 2.0, MEK16
After adding 0.4 g and reacting at a temperature of about 90 ° C. for 3 hours, terminal NC
1604.4 g of an O group-containing urethane prepolymer solution was obtained. On the other hand, IPDA34g, IPA158
While controlling the charging temperature to about 30 ° C. or less, 9.6 g of the above urethane prepolymer solution was added, and the whole was vigorously stirred to obtain a desired cationic urethane resin solution having a terminal NH ₂ group.

Preparation Example of Cationic Acrylic Resin Solution 0.6 g of BPO was added as a polymerization initiator to 30 g of a monomer mixture having the following compounding ratio, and 70 g of IPA (solvent) was charged into a reaction vessel. The monomer containing BPO is dropped and polymerized over about 2 hours while controlling and stirring. After completion of the dropwise addition, 0.6 g of BPO was further added, and the reaction was continued for 2 hours to terminate the reaction. Further, 200 g of IPA was further added as a diluting solvent to obtain a copolymer resin solution having a solid content of 10%. Mixing ratio of monomer for cationic acrylic resin polymerization N, N-dimethylaminoethyl acrylate 0.3 mol Dimethyl methacrylate 0.2 mol Styrene 0.2 mol 2-hydroxyethyl acrylate 0.3 mol The above dye bath treatment liquid K- The raw material [B-
1] to [B-9] were immersed at 20 to 25 ° C. for 10 minutes, and then the raw material was washed with normal water to impregnate the cationic resin.
I got each stock. The raw materials [B-1] to [B-9] impregnated with the cationic polymer compound are immersed in a dye bath containing the following dye bath treatment liquid X at 20 to 25 ° C. for 10 minutes, washed with water, dried and dyed. The obtained synthetic leather was obtained. Treatment liquid X: 90.0 g of methanol 0.5 g of spiron-olene @ 2RH 0.5 g of water 5.0 g of 3% aqueous acetic acid 5.0 g Evaluation of performance of dyed synthetic leather The performance of dyed synthetic leather was measured for dye transferability and 60 degree glossiness. For comparison, the performance in the case of the present invention was compared with the case of dyeing only with the dye bath treatment solution X without using the cationic resin bath of the present invention. Was cut into synthetic leather and 6 × 6 cm ² of Senshokusumi cut into anti migration performance evaluation method 6 × 6 cm ² glass combined [B-2] a white synthetic leather raw shown in the and every one that wetted with tap water Sandwiched between plates, weight 3kg
After a heat treatment at a temperature of 60 ° C. for 20 hours, the migration state (colored state) of the dye from the dyed synthetic leather to the white synthetic leather raw fabric was visually evaluated on a five-point scale. Measurement method for 60 degree gloss.

[0022]

[Table 1]

5: No migration of dye. 4: Very little dye migration. 3: Transfer of the dye is small. 2: Transfer of dye is large. 1: Dye migration is very large.

[0024]

According to the present invention, it is possible to obtain a dyed synthetic leather having improved transfer resistance of a dye, low gloss, and good feeling.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-123083 (JP, A) JP-A-48-36302 (JP, A) JP-A-54-41301 (JP, A) JP-A-63-63 203881 (JP, A) JP-A-48-39780 (JP, A) JP-A-55-40833 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06P 5/00

Claims (3)

(57) [Claims] 1. A synthetic leather raw material is immersed in a cationic resin bath containing 100 parts by weight of a lower alcohol having 4 or less carbon atoms, 0.01 to 10 parts by weight of a cationic resin, and 1.0 to 20 parts by weight of water, Next, lower alcohols 80 to 95 having 4 or less carbon atoms
Of synthetic leather, characterized in that it is dyed with a dye bath containing 0.1 to 10 parts by weight of water-soluble dye, 0.01 to 0.5 parts by weight of oil-soluble dye, 0.01 to 0.5 parts by weight of water-soluble dye. Dyeing method. 2. A synthetic leather raw material is immersed in a cationic resin bath containing 100 parts by weight of a lower alcohol having 4 or less carbon atoms, 0.01 to 10 parts by weight of a cationic resin, and 1.0 to 20 parts by weight of water. Next, lower alcohols 80 to 95 having 4 or less carbon atoms
Synthetic leather dyed with a dye bath containing, by weight, 20 to 5 parts by weight of water, 0.01 to 10 parts by weight of a disperse dye, and 0.01 to 0.5 parts by weight of a water-soluble ionic compound. 3. The dyeing amount is 0.5% per 100 parts by weight of the chromosome.
The dyed synthetic leather according to claim 2, which is not more than 2 parts by weight.