JPH0791785B2 - Dyed synthetic leather - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to dyed synthetic leather, particularly synthetic leather dyed with a reactive dye, and can be used in various applications such as clothing, shoes, bags, and sundries.

[Background technology]

Polyurethane (hereinafter simply referred to as urethane) on the base cloth
Wet or dry dyed synthetic leather having a system skin layer is known. The dyes used for this purpose are 1,2-acid gold-containing dyes (metal complex salt dyes consisting of 2 molecules of dye and 1 molecule of metal), which are currently acid dyes, because they are easy to dye and have good weather resistance. Mostly.

On the other hand, reactive dyes are often used for dyeing natural fibers such as cotton, silk and wool. The characteristic of this dye is that it is strongly bound to the object to be dyed by covalent bond, coordinate bond, etc., so that the dye, that is, color transferability is small, and it is bright and has many deep and bright colors. Is.

[Problems to be Solved by the Invention]

However, since 1,2 acid-containing metal-containing dyes have the property that they easily migrate, conventional dyed synthetic leather will cause color transfer if it is piled up during or after manufacturing as a product such as clothing, shoes, sundries, etc. . This color transfer is very noticeable, especially in the case of a dyed product in which two or more colors are combined, because stacking at different colors is inevitable.

In terms of color, the 1,2 acid-containing metal-containing dyes have a deep color because most of them are slightly dark. However, if a white pigment is added to the base cloth or the adhesive layer (an adhesive is often used to hold the skin layer on the base cloth) in an attempt to make it a bright color, the depth of the color disappears and it becomes cheap. Become.

On the other hand, reactive dyes do not have these drawbacks, but since they are dyed by reaction with functional groups, they cannot be dyed with urethanes that do not have a functional group, and even if they can be dyed with urethanes that have a functional group. Generally, since the number of functional groups that react with reactive dyes is small, the dyeing density is insufficient, and since the dyeing conditions are PH9 to 11.5 and strongly alkaline, they are easily hydrolyzed and practical application is difficult.

Further, particularly in the case of a dyed synthetic leather for clothing having a porous urethane layer under the skin layer, if the porous layer is not dyed, even if the skin layer is dyed, the skin layer may be damaged by scratches or the like. If a white layer appears from the product, it will not be a product. Therefore, in the case of such dyed synthetic leather, it is necessary to dye even the porous layer, but depending on the type of the foaming urethane used in the porous layer, it cannot be dyed with the reactive dye.

It is an object of the present invention to provide a dyed synthetic leather which has no color migration, has many bright colors and deep colors, and has a high dyeing density while maintaining the original leather-like feel and performance.

[Means and Actions for Solving the Problems]

The present invention focuses on the fact that reactive dyes can eliminate all the drawbacks of conventional 1,2-acid-containing dyes, and that certain natural organic polymer powders help improve the apparent dyeing density of urethane. It is intended to achieve the above object.

The dyed synthetic leathers of the present invention are the following two types.

One is to use a reactive dye to fabricate a synthetic leather fabric that has a skin layer made of a mixture of 50 to 98 wt% polyurethane and 50 to 2 wt% of a natural organic polymer powder, which is dyeable with a reactive dye. It is composed by dyeing.

The other is formed by dyeing with a reactive dye a synthetic leather raw fabric further provided with a porous polyurethane layer which can be dyed with a reactive dye under the skin layer.

Materials used for the dyed synthetic leather of the present invention will be described.

As the woven fabric for synthetic leather raw fabric, woven fabrics, knitted fabrics, nonwoven fabrics, urethane-impregnated nonwoven fabrics, and blended products thereof; woven fabrics, knitted fabrics, nonwoven fabrics urethane- impregnated nonwoven fabrics, and blended products thereof, each of which is composed of colored fibers, are used. Of these, base fabrics that are easily dyed with a reactive dye, such as cotton, silk, wool, cupra, nylon, etc., are preferable.

As urethane used for the surface layer of synthetic leather raw fabric,
Any dye that can be dyed with a reactive dye, that is, one that has a functional group capable of reacting with a reactive dye can be used. Of course, reactive dyes that decompose or are modified under the dyeing conditions (PH9 to 11.5) cannot be used. It should be noted here that there are many types of urethane, and even if they have a functional group that reacts with a reactive dye, many are hydrolyzed under dyeing conditions, that is, in the high PH range. Therefore, the urethane for epidermis used in the present invention must be one that can be dyed with a reactive dye without being modified or decomposed under dyeing conditions. Examples of such urethanes include polyether type, polycarbonate type (these are used as a solution or dispersion of an organic solvent or water), polyester type (used as an aqueous solution or an aqueous dispersion),
And urethanes such as mixed diols thereof and the like.

The commercial products of these dyeable urethanes are as follows.

Organic solvent-based products; Resamine ME-8105LP (polyether type) made by Dainichi Seika Co., Ltd. Sanprene SP200D (mixed system of polyether type, polyester type, etc.) made by Sanyo Kasei Co., Ltd. Crisbon 3116S (polycarbonate type) made by DIC Toyo Polymer Co., Ltd. Made by Petal 9060, 7116 (polycarbonate type) Water-based product; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. Superflex E4000 (polyether type) Superflex E2000 (polyester type) In addition, even urethane that can be dyed with a reactive dye generally has a reactive functional group Since the amount is small, the dyeability is insufficient.

On the other hand, the raw material urethane of the porous urethane for the porous layer may be one that can be dyed with a reactive dye, as in the case of the skin layer. Of course, a dye that decomposes or is modified under the dyeing conditions cannot be used. Examples of urethanes suitable for the porous layer include polyether-based, polycarbonate-based, polyester-based (preferably polyester-based crosslinking agent-based polyesters from the viewpoint of preventing fatigue), and mixed diol-based urethanes thereof. These are preferably used in aqueous emulsion. Examples of such aqueous commercial products include Superflex E4000 (polyether type) and E2000 (polyester type) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and Resamine UF138 (modified) (polyester type) manufactured by Dainichiseika.

As urethane suitable for dyeing with reactive dyes,
Both the urethane for the skin layer and the urethane for the porous layer are preferable because there is little change in the texture and little deterioration when looking at the elongation before and after dyeing as a film.
This elongation is 100% ± 20% (according to JIS-Z1702) after the dyeing of the urethane film in the reactive dye aqueous solution at a temperature of 90 ° C. for 1 hour, compared with the one before the dyeing step, All the dyeable urethanes exemplified above are within this elongation range.

The natural organic polymer powder used for the surface layer of the synthetic leather raw fabric may be any one that can be dyed with a reactive dye, like urethane and porous urethane. Of course, a reactive dye which decomposes or is modified under the dyeing condition cannot be used. This natural organic polymer powder is mainly used for improving the dyeability of urethane in the skin layer. Such natural organic polymer powders include leather powder, chitin powder, silk powder, gelatin powder, casein powder, wool powder, collagen powder,
Cellulose powder and the like, and preferably leather powder are mentioned. When these powders are added to the epidermis layer, not only the dyeing property is improved, but also the tackiness is reduced, the moisture absorbing / releasing property is imparted, and the surface roughness is imparted with a good texture. The amount of these natural organic polymer powders added to the skin layer is in the range of 50 to 2 wt% with respect to 50 to 98 wt% of urethane. If it is less than 2%, the effect of addition cannot be expected sufficiently, and if it is more than 50%, it becomes brittle and cannot be used. The particle size of the powder is appropriately equal to or less than the thickness of the wet coating film at the time of coating in consideration of the formation of the skin layer by coating, that is, forming into a film or sheet, but preferably the dry coating film of the skin layer is formed. It is equal to or less than the thickness, more preferably 1/3 or less. Generally, the skin layer thickness is 20 to 50 μm for clothing, and 20 to 200 μm for shoes, furniture, or car seats, so the particle size is 200 μm.
m or less, preferably 70 μm or less, more preferably 10 μm
It is the following.

Among the above natural organic polymer powders, as a specific example of leather powder, fine leather powder (obtained by the method described in JP-A-63-156552, for example) is further jet-milled to have an average particle diameter D.
Re-finely pulverized to ₅₀ = 7 μm or less, as silk powder, silk powder IM or P20 manufactured by KANEBO SPAN SILK LTD and having D ₅₀ of 8 μm or less, and as gelatin powder, described in JP-A-1-294740. D ₅₀ = 6 μm or less, and as cellulose powder, KC Flock manufactured by Sanyo Kokusaku Pulp Co., Ltd.
Examples include W400 and W500.

If necessary, natural organic polymer powders and fillers used in the skin layer can be added to the porous layer. In the present invention, it is preferable to add a natural organic polymer powder also to the porous layer, and in this case, it is possible to give the porous layer an effect such as an improvement in dyeability, an improvement in moisture absorption and desorption, and a resistance to fatigue. . Further, when a filler is added, the porous layer can be provided with an effect of preventing settling. Examples of the filler include talc, calcium carbonate, inorganic filler such as metal oxide powder, and the like. The amount of the natural organic polymer powder or filler added is preferably 30% or less, and if it is too large, it becomes hard and brittle and difficult to stretch. Further, when a layer is formed by coating, the viscosity of the coating liquid becomes too high, which makes uniform coating difficult, resulting in a decrease in commercial value. The particle size of the natural organic polymer powder or the filler is preferably the same as in the case of the skin layer, but may be different, or may be a different combination or mixed system.

The reactive dye for dyeing the synthetic leather raw fabric made of the above materials may be for medium temperature or high temperature, but is preferably cellulose or wool depending on the application. Such reactive dyes include pyrimidine-based, triazine-based, vinyl sulfone-based, quinoxaline-based, monoazo-based,
Examples include a single type such as a disazo type and a complex type such as a vinyl sulfone-triazine type, a monoazo-vinyl sulfone type, and a phthalocyanine-vinyl sulfone type. Table 1 shows an example of commercial products of these reactive dyes.

In addition, typical structural examples of various reactive dyes are shown below.

Vinyl sulfone type (vinyl sulfone group-SO as reactive group
₂ CH = CH ₂ or sulfatoethylsulfonyl group —SO ₂ CH ₂
With CH ₂ OSO ₃ H): CI Reactive Blue 19 CI Reactive Black 5 Triazine type [Reactive triazine ring Having reactive groups (Cl, F, etc.): ・ Examples of dichlortriazine type CI Reactive Orange 4 ・ Examples of monochlorotriazine CI Reactive Orange 13 ・ Example of monofluorotriazine CI Reactive Orange ・ Examples of other triazine-based reactive dyes Pyrimidine system [Reactive pyrimidine ring (Any or all of X, Y and Z are reactive groups such as Cl and F)
]: A typical example is a triazine system in which the triazine ring is changed to a pyrimidine ring.

Quinoxaline type (as a reactive group With): CI Reactive Red 41 Phosphonic acid type (as a reactive group With): CI Reactive Red 177 Acrylic acid type (as a reactive group With): CI Reactive Red 29 Complex type (with two different reactive groups): CI Reactive Red 194 Next, a method for producing the dyed synthetic leather according to the present invention will be described.

First, in order to produce a synthetic leather original fabric for dyeing, a skin layer of a dyeable urethane-dyeable natural organic polymer powder mixture is formed on a base fabric. As a method of forming the skin layer, a direct coating method,
Any known method such as a transfer coating method, a gravure coating method, or a spray coating method can be adopted, but the transfer coating method is preferable.

In the case of the direct coating method, as shown in FIG. 1, the coating liquid 2 in which the dyeable natural organic polymer powder is dispersed in the dyeable urethane solution is applied to the base cloth 1 to a desired thickness by the doctor knife 3 or the like. After coating and drying with dryer 4,
The synthetic leather original fabric 7 is obtained by cooling with the cooling means like the cooling cylinder 6 and providing a skin layer (not shown).
In addition, 5 is a rubber roll for conveyance.

There are various transfer coating methods as follows.

A resin film is formed on release paper in advance, and this is laminated on a base cloth using an adhesive.

While the surface of the resin film is tacky without using an adhesive, it is pressure-bonded to the base cloth.

The surface of the resin film is heated to give tackiness without using an adhesive, and this is pressure-bonded to the base cloth.

In the case of this transfer coating method, first of all, the coating solution 12 as described above is applied to the release paper 10 by a knife roll 11 or the like to a desired thickness, and the dryer 13 is used. And dried with a cooling roll 14 or the like to form a resin film 15 serving as a skin layer on the release paper. Next, on this resin film, after applying the adhesive 16 with a knife roll 17 or the like, a base fabric 18 separately supplied on it is laminated by a nip roll 19, and after drying with a drier 20, By cooling with a cooling roll 21 or the like, a synthetic leather raw fabric 22 having a skin layer can be obtained.

In the case of the gravure coating method, as shown in FIG. 3, the coating solution 31 as described above is applied on the base fabric 30 by the gravure coater 32 and dried by the dryer 33 to form a skin layer (not shown). By forming the, the synthetic leather raw fabric 34 is obtained.

Further, in the case of the spray coating method, the above-mentioned coating liquid is sprayed by the spray 42 (41 indicates a sprayed state) on the base cloth 40, adhered, and dried by the dryer 43,
By cooling with a cooling roll 44 or the like to form a skin layer (not shown), a synthetic leather raw fabric 45 is obtained.

The synthetic leather raw fabric thus prepared has a skin layer directly on the base fabric or through an adhesive layer, but in the case of producing a synthetic leather raw fabric having a porous urethane layer under the skin layer. Is a mechanical foaming urethane composition containing a dyeing urethane for a porous layer, a foaming agent, etc.
Double (volume), preferably 1.5 to 4 times, air-foamed, apply this on the base cloth, 60 to 140 ℃, preferably 60 to 120 ℃
To dry. If the degree of foaming is less than 1.2 times, the flexibility and porosity due to foaming will decrease and become hard and rubber-like,
On the other hand, if it is more than 5, the strength of the porous material is lowered, and the porous material is likely to peel off and cannot be used. If the drying temperature exceeds 140 ℃,
Drying rates are likely to vary widely within the coating layer, which does not result in a stable porous layer. If the drying temperature is lower than 60 ° C., the drying speed will be slow, the foamed layer will be settled, and the drying step will become a bottleneck industrially, resulting in high cost.

The foamable urethane composition for forming a porous layer generally comprises 60 to 90 wt% urethane for a porous layer, 2 to 7 wt% foaming agent, and 0 foaming agent.
~ 10wt%, foam stabilizer 0.5-1.5wt%, thickener 0-5wt
%, Cross-linking agent 0 to 15 wt%, said natural organic polymer powder 0 to 20
wt% and 0 to 20 wt% of filler are dissolved or dispersed in water. Here, the total amount of the natural organic polymer powder and the filler is preferably 30 wt% or less from the viewpoint of solution viscosity and uniform foaming property. Further, if it exceeds 30 wt%, the product tends to be hard and brittle.

As a foaming agent, a score min former made by Daiichi Kogyo Seiyaku Co., Ltd.
There is RF.

Examples of the foaming agent include freon and water.

Examples of the foam stabilizer include Fine Gum G270 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

Examples of the thickener include Superflex VF manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

Examples of the cross-linking agent include F8914 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

Examples of the filler include calcium carbonate and talc.

As the coating method of the urethane composition after foaming, the same coating method as in the case of the skin layer can be adopted, but a direct coating method is usually used. Coating amount is solid content
50 to 200 g / m ² is suitable. The thickness of the porous layer thus formed varies depending on the application, but is generally 20 to 1000 μm.
It is a degree.

After the porous urethane layer is formed on the base fabric as described above, the skin layer is further formed thereon by the coating method as described above, whereby a synthetic leather raw material having a porous urethane layer under the skin layer. You can get the opposite.

Next, a method for dyeing a synthetic leather raw fabric will be described.

The dyeing material is first refined. This is dirt on the surface, glue,
This is a preparatory step for removing oils and fats and the like so that the dye easily penetrates and uneven dyeing is not performed. In this process, the raw fabric is a surfactant (usually 0.05-0.2wt%), a penetrating lubricant (usually 0.05-0.5wt%) and a leveling agent (usually 0.1-0.5w).
t%) in an aqueous solution of approximately 2 at room temperature to 95 ° C.
Wash for 0 to 60 minutes.

The raw material after smelting is washed with water and dyed in the next dyeing step. The dyeing step is performed by first adding the dye and the dyeing aid while raising the temperature of the dyeing aid aqueous solution containing the dyeing raw fabric.
When the dyeing solution reaches the fixing temperature of the dye, it is kept at this temperature for a certain period of time and then cooled. The dyeing solution contains a reactive dye (usually 0.5 to 10 wt%) and a dyeing aid (usually 2.5 to 10 wt% based on the weight of the material to be dyed) as essential components.
Dispersing leveling agent if necessary (usually 0.05 to 1.
0 wt%), softener in the bath (usually 0.05 to 0.1 with respect to the dyeing solution)
5wt%), dye fixing agent (usually 0.1-0.4w for dyeing solution)
t%) is added.

Next, the thus dyed original fabric is washed by a soaping (washing) process. In the soaping process, a detergent (usually 0.02 to 0.05 wt%) is used as a soaping agent in an aqueous solution.
It is carried out by immersing the dyeing raw fabric in the temperature range of room temperature to 95 ° C. for about 10 to 30 minutes to remove the unfixed excess dye adhered in the dyeing process. If it cannot be removed sufficiently, repeat again.

Finally, the wet dyeing raw fabric after soaping undergoes a finishing process to give a certain tension by a tenter if necessary,
It is dried in the drying process. The drying step is performed by squeezing the wet dyeing raw fabric with a mangle to remove excess water, and then hanging it over a tenter and passing it through a drier to dry. The drying temperature at this time is 130 ° C or lower, preferably 120 ° C or lower.

When it is dried at 130 ° C or higher, the urethane of the skin layer or the porous layer is decomposed, or the temperature of the dryer is uneven and the temperature becomes high locally, so that the urethane is melted or deformed.
Either before or after the drying step may be performed, but a rubbing step and / or a surface treatment step may be performed. Further, the finishing step may be carried out in the presence of a water repellent, oil repellent, antistatic agent, softening agent, texture modifier, disaster prevention agent and the like.

The surfactants, permeation wetting agents, leveling agents, dyeing assistants, dispersion leveling agents, in-bath softeners, dye fixing agents and the like used in the above dyeing methods may all be commonly used.

FIG. 5 shows a typical manufacturing process of the dyed synthetic leather according to the present invention.

〔Example〕

 The present invention will be described below with reference to examples.

Examples 1 to 2 and Comparative Examples 1 to 3 Production of Dyeing Synthetic Leather Raw Fabric Each coating liquid shown in Table-1 was stirred at 500 rpm for 1 hour,
After mixing, suction and degassing were performed with an aspirator. The content of each leather powder of coating liquids A, B, C, D, E is 10 wt%, 20 wt%, 1 wt%, 60 wt% in terms of solid content with urethane.
%, 0 wt%.

120 g / m ^{2 of} each coating solution was applied to release paper (using a semi-matte tone of DN-TP series manufactured by Dai Nippon Printing Co., Ltd.) using the transfer coating device shown in Fig. ^{2 and} dried at 110 ° C for about 90 seconds. , A 20 μm thick urethane film to be the skin layer is formed, and an adhesive (Sanprene LQ manufactured by Sanyo Kasei Co., Ltd.
X5: 50 g and Sanprene LOS-A: mixing a 50 g, was stirred, to prepare) 100 g / m ² was applied degassed, further thereon by plain nylon taffeta base fabric (210 denier fibers by a nip roll Plain weave) is laminated and adhered, and dried at 100 ° C. for about 90 seconds, and five kinds of synthetic leather original fabrics for dyeing (these original fabrics are G-based for coating liquids A, B, C, D and E, respectively) A, G
-B, G-C, G-D and G-B. ) Was produced.

Dyeing of synthetic leather original fabric First, for each original fabric for dyeing, 2 g of non-ionic surfactant (Sorge AB manufactured by Meisei Chemical Co., Ltd.), non-ionic surfactant (Meisserin H100 permeation wetting agent manufactured by Meisei Chemical Co., Ltd.) At 60 ° C in an aqueous solution prepared by dissolving 0.5 g of nonionic surfactant (Meisei Chemical Industry Co., Ltd. degassing penetrant Mynex TH) in water 1.
It was refined for 20 minutes and then dehydrated easily.

Next, each raw material after refining is treated with a pyrimidine-based reactive dye (Sandoz
Drimarene Turquoise X-B) (30 g), anhydrous Glauber's salt (60 g) and a dyeing aid (Revatol S from Sandoz) in a dyeing solution dissolved in water 1 were dyed at 40 ° C for 10 minutes, and 15 g of soda ash was added. For 10 minutes, then raise the temperature to 60 at 85-90 ° C.
It was fixed for a minute. Subsequently, the dyed stock was soaped for 20 minutes in a boiling soaping solution (Sandopur RSK Liquid manufactured by Ciba-Geigy) in which 1 g of sodium tripolyphosphate was dissolved in 1 water, washed twice with water, and squeezed with a mangle to remove excess. After removing water, it was dried at 100 ° C. The obtained five kinds of dyed synthetic leather are the same as the original synthetic leather for dyeing G-A, G
-B, G-C, G-D and G-E respectively, Example 1,
Example 2, Comparative Example 1, Comparative Example 2 and Comparative Example 3 are used.

Comparative Examples 4 to 6 Synthetic raw fabrics for dyeing G-A, G-B and G-E prepared in Examples 1, 2 and 3 were 20 g of ammonium sulfate and a dyeing aid (manufactured by Ciba-Geigy). Albegal SW) 20g water 1
After pretreatment at 30 ° C for 10 minutes in a solution dissolved in
Acid gold dye (Ciba-Geigy Lanacron BlackS-R)
Add 30 g and 5 g acetic acid to make a dyeing solution.
It was dyed at 10 ° C. for 10 minutes and then fixed at 95 ° C. for 45 minutes. The obtained three kinds of dyed synthetic leathers correspond to the used synthetic leather raw fabrics G-A, G-B, and G-E, respectively,
These are Comparative Example 4, Comparative Example 5 and Comparative Example 6.

Table 2 shows the relationship between the dyed synthetic leathers produced in Examples 1 to 2 and Comparative Examples 1 to 6, the coating liquid used and the dyes used, and the results of the performance tests of these dyed synthetic leathers. It shows in Table-3.

The test method is as follows.

Dyeability: Evaluation was made based on the degree of dyeing in Comparative Example 5.

◯ means good, Δ means slightly light, and x means hardly dyed.

Color migration: Each synthetic leather raw material before dyeing and after dyeing is fixed with a rubber band on a glass tube with a diameter of 3 to 5 cm so that the skin layers contact each other, and in a constant temperature bath at 70 ° C to 95% RH. Leave for 3 days.

After cooling, the epidermis is observed to check for color transfer.

○ means good, △ means lightly colored, and × means that the entire surface is clearly transferred.

Tack feeling: Feeling touched by hands, and contacting the skin layers of each dyed synthetic leather with each other, the slipperiness of the skin layers was evaluated.

O indicates a dry touch that is slippery, Δ indicates that it is difficult to slip, and x indicates that it is hard to slip and is not dry touch.

Moisture absorption and release: Double-sided tape with a width of 15 mm is attached to the peripheral edge of a 130 mm square aluminum plate, which is conditioned for 24 hours in a constant temperature bath at 23 ° C to 50% RH. Paste on the side,
The periphery of the skin layer side is sealed with a 15 mm wide vinyl tape to make the exposed surface of the skin layer approximately 100 mm square.

Next, in the case of hygroscopicity measurement, this sample (with aluminum plate) is conditioned for 24 hours in a thermostat at 23 ° C to 30% RH, the weight (reference weight) W ₀ is measured, and this condition is further adjusted. Measure the weight W ₁ of the same sample left for 24 hours in a constant temperature bath at 23 ° C to 80% RH or in a container containing a saturated aqueous solution of ammonium sulfate in the same atmosphere.

On the other hand, in the case of moisture release measurement, the weight (reference weight) of the sample when conditioned for 24 hours in a constant temperature bath at 23 ° C. and 80% RH or a container containing an ammonium sulfate saturated solution in the same atmosphere W ₀
Of the same sample adjusted to this condition
Measure the weight after leaving it in a 30% RH constant temperature bath for 24 hours.

Each weight is measured up to the unit of 1 mg, and in principle, the measurement is performed in an atmosphere of 23 ° C to 50% RH.

From the above measured values, the hygroscopicity (as the rate of moisture absorption or the amount of moisture absorbed per 1 m ² ) and the moisture release rate (as the rate of moisture released or the amount of moisture released per 1 m ² ) can be obtained from the following equations.

(However, W ₀ ... standard weight, W ₁ ... weight after standing for 24 hours, S ... exposed surface area of the sample) ○ is 4 g / m ² or more for both hygroscopicity and moisture desorption, △ is also 3
Similarly, ~ 4 g / m ² and × indicate 3 g / m ² or less.

Examples 3 to 6 and Comparative Examples 7 to 14 Production of Dyeing Synthetic Leather Raw Fabric Each foamable coating liquid shown in Table 4 (viscosity 38000 cps)
The Stoke foaming machine FP-II-C and coating head
Using a device combined with CT-IV, foam it 3.0 times and apply it to a plain nylon knit base fabric using the direct coating device shown in Fig. 1 so that the dry weight will be 100 g / m ² and 120 ° C. And dried for 2 minutes to form a porous urethane layer having a thickness of 600 μm. 3 having a porous layer thus obtained
The seed fabric is the foamable coating liquid a, b and c used.
To Ka, Kb, and Kc, respectively.

Next, according to the same method for producing a synthetic leather raw fabric for dyeing as in Examples 1 and 2, for (1) the base fabric Kb, the coating liquids A, B, C, D and E shown in Table 1 were added. Five kinds of synthetic leather stocks for dyeing (applied on the porous layer, the same applies below) (each of these stocks corresponds to the coating liquids A, B, C, D and E used, Gb -A, Gb-B, Gb-C, Gb-D, and Gb-E) are prepared, and (2) the base fabric Ka is applied with the coating liquid B to produce a synthetic leather original fabric for dyeing. Ga-B was prepared, and (3) the coating solution B was also applied to the base cloth Kc to prepare a synthetic leather original fabric Gc-B for dyeing.

Dyeing of synthetic leather original fabrics 7 types of original fabrics Gb-A, Gb-B, Gb-C, Gb-D, Gb-E, Ga-B and Gc- prepared as above as original fabrics for dyeing. Using B, 60g of anhydrous Glauber's salt changed to 80g, and 15g of soda ash to 20g
7 according to the same dyeing method as in Examples 1 and 2 except that
A variety of dyed synthetic leathers were made.

These dyed synthetic leathers are used for the original fabrics Gb-A, Gb-B, Gb-
Corresponding to C, Gb-D, Gb-D, Gb-E, Ga-B, and Gc-B, Example 3, Example 4, Comparative Example 7, Comparative Example 8, Comparative Example 9, and Example 5 respectively. And Example 6.

Comparative Examples 10 to 14 Original fabrics Gb-A and Gb prepared in Examples 3 to 6 as original fabrics for dyeing
Five kinds of dyed synthetic leathers were produced by the same dyeing method as in Comparative Examples 4 to 6 except that -B, Gb-E, Ga-B and Gc-B were used and the pyrimidine reactive dye 30g was changed to 40g. . These dyed synthetic leathers are used for the original fabrics Ga-A, Gb-B, Gb-E, Ga-B and Gc.
Comparative example 10, comparative example 11, comparative example 12, comparative example 13 and comparative example 14 correspond to -B, respectively.

Table 5 shows the relationship between the dyed synthetic leathers produced in the above Examples 3 to 6 and Comparative Examples 7 to 14 and the foamable coating liquid used, the coating liquid used and the dyes used, and these dyed synthetic leathers. Table 6 shows the results of the performance tests of the above.

Dyeability: The degree of dyeing in Example 3 was evaluated. The meanings of ○, △, and × are the same as in Table-3.

Moisture absorption and desorption: The test method is the same as in Table 3, but ○ indicates 6 g / m ² or more, △
Represents 4 to 6 g / m ² , and x represents 4 g / m ² or less.

Settle and resin deterioration: Store the dyed product in 70 ° C-95% RH for 3 weeks (equivalent to 3 years), and check the thickness change. When the amount of change in thickness was within 10% of the initial thickness, it was evaluated as ○, within 20% as Δ, and when 20% or more as ×. After the same test, when there was no resin deterioration, it was evaluated as ◯, and when it was evaluated as ×.

〔The invention's effect〕

According to the present invention as described above, those having a porous layer,
It is possible to provide a dyed synthetic leather which does not have a color transfer property, has many bright colors and deep colors, and has a high dyeing density while maintaining the original leather-like feel and performance.

[Brief description of drawings]

1 to 4 are schematic views of a direct coating device, a transfer coating device, a gravure coating device and a spray coating device, respectively, which can be used for producing a synthetic leather raw fabric for dyed synthetic leather according to the present invention, and FIG. It is a typical manufacturing process drawing of dyed synthetic leather according to the invention. 1,18,34,40 …… Base fabric, 2,12,31,41 …… Coating liquid (however 41 is sprayed), 3 …… Doctor knife, 4,13,2
0,33,43 …… Dryer, 6,14,21,44 …… Cooling cylinder or roll, 7,20,30,45 …… Synthetic leather stock, 10 …… Release paper, 1
1,17 …… Knife roll, 15 …… Resin film resin film for release layer, 16 …… Adhesive, 19 …… Nip roll, 32 ……
Gravure coater, 42 ... spray.

Claims (4)

[Claims] 1. A 50 to 98 wt% polyurethane and 50 to 2 wt% natural organic polymer powder, each of which can be dyed with a reactive dye on a base cloth.
A dyed synthetic leather, which is obtained by dyeing a synthetic leather raw fabric having a skin layer made of a mixture of the above with a reactive dye. 2. The dyed synthetic leather according to claim 1, wherein the natural organic polymer powder is leather powder. 3. A porous polyurethane layer which can be dyed with a reactive dye on a base cloth, and a porous polyurethane layer which can be dyed with a reactive dye on the porous polyurethane layer, respectively.
Polyurethane 50-98wt% and natural organic polymer powder 50-2wt
% Synthetic dyed leather, which is obtained by dyeing a synthetic leather raw fabric provided with a skin layer made of a mixture of 1% with a reactive dye. 4. The dyed synthetic leather according to claim 2, wherein the natural organic polymer powder is leather powder.