JP3017665B2 - Synthetic leather and manufacturing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic leather having an excellent deodorizing property capable of removing malodors, and more particularly to ammonia, trimethylamine, methyl mercaptan, hydrogen sulfide, etc., which are main components of malodors. The present invention relates to a synthetic leather exhibiting an excellent deodorizing effect and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, synthetic leather having a polyurethane resin film layer is excellent in texture, appearance, physical properties, etc., and is therefore widely used as a material for clothing, gloves, bags, bags, shoes, furniture, vehicles and the like. Used in

[0003]

By the way, various products obtained from the above-mentioned synthetic leather are sometimes used in places where odors are accumulated or generated, but synthetic leather has a deodorizing effect. And it was not possible to remove the odor. In addition, in order to impart a deodorizing effect to polyurethane synthetic leather, it is conceivable that the outermost skin layer of the synthetic leather contains a deodorant such as activated carbon or ferrous sulfate, but since activated carbon is black, The resulting synthetic leather is limited to black or dark colored ones.In addition, ferrous sulfate is easily discolored to brown by oxygen in the air and impairs the color tone of the polyurethane synthetic leather. Similarly, it is limited to black or dark colors, and any of them is unsuitable as a material for products requiring various beautiful colorings.

Therefore, even if the polyurethane synthetic leather contains a deodorant, it does not color the synthetic leather, can be easily colored to an arbitrary color, and absorbs the odor from the surroundings for a long time to remove the odor. There has been a demand for a polyurethane synthetic leather having a deodorant property that can be removed.

The present invention has been made to solve the above-mentioned demands of the prior art, and is intended to provide a polyurethane synthetic leather which can be colored in an arbitrary color tone and is excellent in deodorant properties and a method for producing the same. The purpose is to provide.

[0006]

Means for Solving the Problems The synthetic leather of the present invention is a synthetic leather comprising a single layer or a plurality of polyurethane resin coating layers laminated on the surface of a fiber base via a polyurethane resin adhesive layer. And at least one layer selected from a polyurethane resin film layer and a polyurethane resin adhesive layer that does not contain a deodorant, and is provided with a plurality of openings penetrating synthetic leather. is there. Further, the method for producing a synthetic leather of the present invention is a method for producing a synthetic leather by sequentially laminating a single layer or a plurality of polyurethane resin coating layers via a polyurethane resin adhesive layer on the surface of a fiber substrate such as a knitted fabric, a woven fabric, or a nonwoven fabric. A method for producing synthetic leather in which a heated metallic needle is inserted from the back side of the synthetic leather after the formation, and a plurality of through-holes are provided on the surface of the synthetic leather, wherein the polyurethane is not the outermost skin layer. At least one layer selected from a resin film layer and a polyurethane resin adhesive layer contains a deodorant.

Examples of the fiber base material used for the synthetic leather of the present invention include knitted fabrics, woven fabrics, and nonwoven fabrics made of fibers having a single yarn fineness of 5 denier or less. Are preferred. The nonwoven fabric is a nonwoven fabric that has been entangled by a needle punch or a high-speed fluid flow, and the nonwoven fabric is provided with an elastic polymer such as a polyurethane resin or a synthetic rubber in advance, or is not provided. Can be used.

The fibers constituting the fiber base material include synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyolefin, and polyvinyl alcohol; natural fibers such as cotton and hemp; and recycled fibers such as rayon, swoof, and acetate alone or in combination. Or a multicomponent fiber modified into ultrafine fibers by dissolving and removing at least one component or splitting a bicomponent fiber.

The polyurethane resin used in the present invention comprises:
A polymer diol having an average molecular weight of 500 to 4000, for example, at least one diol selected from polyester diol, polyether diol, polyester ether diol, polycaprolactone diol, polymethyl valerolactone diol, polycarbonate diol, and an organic polyisocyanate For example, at least one organic polyisocyanate selected from the group of aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate having a cyclic group and the like, and a low molecular compound having at least two active hydrogen atoms are chained. Extender, for example, obtained by reacting with at least one chain extender selected from the group of aliphatic diols, alicyclic diols, aliphatic diamines, alicyclic diamines, hydrazine derivatives and the like. It is a polyurethane resin. These polyurethane resins may be modified polyurethane resins obtained by reacting amino acids, silicone, fluorine and the like.

The composition of the above polyurethane resin is appropriately selected from those satisfying various properties such as hand, hydrolysis resistance, light deterioration resistance and discoloration resistance, depending on the intended purpose of the synthetic leather to be obtained. Can be. Preferably, a two-component polyurethane resin is used as the polyurethane resin used for the adhesive layer, and a one-component polyurethane resin is used as the polyurethane resin used for the coating layer.

[0011] The polyurethane resin forming the adhesive layer and the film layer may be added to various known additives such as a coloring agent, a crosslinking agent, a stabilizer, a natural powder, a filler and the like. It is dissolved in an appropriate solvent together with the agent to form a polyurethane resin solution.

As the organic solvent for dissolving the above polyurethane resin, preferably, for example, methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone,
Diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, etc.
Acetone, cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and any ratio thereof Mixtures and the like can also be used.

In the synthetic leather of the present invention, as the deodorant contained in the above polyurethane resin, a colored deodorant such as activated carbon or ferrous sulfate can be used, but more preferably a white or substantially colorless deodorant is used. It is a odorant. In addition, it must not deteriorate the quality of the polyurethane resin, and must effectively absorb malodors such as ammonia odor, amine odor, mercaptan odor, and hydrogen sulfide odor generated in general homes. Is preferred.

The deodorant used in the synthetic leather of the present invention is particularly preferably formed by binding at least one acid selected from ascorbic acid and oxypolybasic acid or a salt thereof to manganese (II) ion. Compound (hereinafter sometimes simply referred to as "manganese (II) -organic acid compound")
Is mentioned.

Among the above-mentioned manganese (II) -organic acid compounds, specific examples of the compound that forms manganese (II) ions include manganese such as manganese sulfate, manganese nitrate, manganese chloride, manganese bromide, and manganese iodide. II)
Inorganic salts or manganese (II) organic salts such as manganese acetate, manganese gallate, manganese malate, manganese fumarate and the like can be mentioned, with manganese sulfate and manganese chloride being particularly preferred.

Ascorbic acid which binds to manganese (II) ions is known as L-vitamin C.
Even ascorbic acid, also referred to as D-araboascorbic acid or D-erythorbic acid, has a poor physiological activity such as vitamin C, but is used even if D-ascorbic acid is easily used because of its easy synthesis. Although it is possible, L-ascorbic acid is particularly preferred. Further, instead of ascorbic acid, an alkali metal salt such as sodium or potassium or an ammonium salt of ascorbic acid can be used.

The oxypolybasic acid is not particularly limited as long as it is soluble in water. For example, citric acid, isocitric acid, lactic acid,
Examples thereof include tartaric acid, tartronic acid, malic acid, gluconic acid, oxybenzoic acid, salicylic acid, and alkali metal salts and ammonium salts thereof. Citric acid is preferred from the viewpoint of practicality such as cost. These ascorbic acid and oxypolybasic acid form a stable compound in an aqueous solution by coordinating or chelating with manganese (II) ion.

The manganese (II) -organic acid compound is
After adding an appropriate amount of one or more organic acids selected from ascorbic acid and oxypolybasic acid to an aqueous solution of one or more compounds that form divalent manganese ions, and combining the two components, spray drying and freezing It is obtained by pulverization by means such as drying. At this time, by using ascorbic acid and oxypolybasic acid in combination as organic acids,
Synthetic leather having a more excellent deodorizing effect on ammonia and hydrogen sulfide, which are one of the main components of the offensive odor, can be obtained. Further, the powdered manganese (II) -organic acid compound may be further finely powdered by a known means.

In a manganese (II) -organic acid compound,
The component ratio of manganese (II) ion to organic acid is not particularly limited, but when ascorbic acid is used alone, the molar ratio of manganese (II) ion to 1 ascorbic acid is 0.1%. Is preferably in the range of ~ 1.0,
More preferably, it is in the range of 0.25 to 0.75 ascorbic acid with respect to manganese (II) ion 1. When the acid component is an oxypolybasic acid alone, the molar ratio of manganese (II) ion to 1 corresponds to 0.5 to 1.
0 is preferable, and manganese (II) ion 1 is more preferable.
Is 0.75 to 1.0.

Further, when ascorbic acid and polybasic acid are used in combination as the organic acid, manganese (I
I) The total of ascorbic acid and oxypolybasic acid is preferably 0.5 to 1.5, more preferably 0.75 to 1.25, with respect to ion 1. It is.

The amount of the deodorant used in the present invention is appropriately selected depending on the kind of the deodorant to be added, the position of the polyurethane resin layer to be added, and the like. For example, when the manganese (II) -organic acid compound is used, it is preferably added in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of a resin solid content such as a polyurethane resin. Manganese (I
If the amount of the (I) -organic acid compound is too small, the deodorizing effect which is the main object of the present invention is not sufficiently exerted, and if it is too large, the deodorizing effect is improved to some extent. The strength is significantly reduced, and the texture becomes hard. When a deodorant such as activated carbon or ferrous sulfate is used, 1 to 5 parts by weight per 100 parts by weight of resin solids such as polyurethane resin.
It is preferable to add about 0 parts by weight.

In the synthetic leather of the present invention, a foamed layer or a non-foamed layer may be provided between the fiber base material and the polyurethane resin film layer. This foamed layer may be any of a wet porous layer, a dry porous layer and a dry foamed layer of a polyurethane resin. These foamed layers are formed by a known method such as a method of forming a foamed layer directly on a fiber base material or a method of forming a foamed layer on a fiber base material via an adhesive.

The particle size of the deodorant used in the present invention is appropriately selected depending on the type of the deodorant used. For example,
When a manganese (II) -organic acid compound is used, the average particle diameter of the manganese (II)-organic acid compound is 50 μm.
Or less, preferably 30 μm or less. Manganese (II)
-If the average particle size of the organic acid compound is too large, it causes streaks when forming the polyurethane resin layer.

Next, a method for producing the synthetic leather of the present invention will be described. Here, as a method for producing the synthetic leather of the present invention, a production method by a paper casting method will be described as an example.

First, a one-component polyurethane resin solution is applied to the surface of a release paper having an uneven pattern on the surface by means of a knife coater or the like, and dried to gel the polyurethane resin to form a coating layer. Further, an adhesive composed of a two-component polyurethane resin solution containing a manganese (II) -organic acid compound, a crosslinking agent and an accelerator is applied on the film layer by means of a knife coater or the like. Next, the fiber base material is placed on this adhesive, pressed and pressed, dried and wound up, and kept warm for several days for reaction aging to complete the reaction of the polyurethane resin adhesive and adhere to the fiber base material. Complete adhesion between the layer, the adhesive layer and the coating layer. Thereafter, by peeling off the release paper, the uneven pattern on the surface of the release paper is transferred to the polyurethane resin film layer, and a synthetic leather having an appearance very similar to the surface of natural leather is obtained. When the manganese (II) -organic acid compound is mixed with the polyurethane resin solution, the manganese (II) -organic acid compound is insoluble in the organic solvent, and therefore, is uniformly dispersed in the solvent used for diluting the polyurethane resin. After that, it is mixed with the composition of the polyurethane resin solution. Thereafter, a heated metallic needle is inserted from the back side of the synthetic leather to provide a plurality of openings through the synthetic leather on the surface of the synthetic leather.

In the above-mentioned method for producing synthetic leather, the coating amount for obtaining each layer can be varied in a wide range depending on the intended use, and is in the range of about 10 to 1500 g / m ² (mixed liquid). Selected as appropriate. The gelation and drying for obtaining each polyurethane resin layer may be the same as those in the prior art, and may be performed, for example, at a temperature of about 50 to 150 ° C. for several minutes to several hours (however, a two-component polyurethane resin). In the case of (1), synthetic leather having excellent properties can be obtained by further drying for several tens of hours.

In the above-described method for producing synthetic leather, the shape of the opening provided on the surface of the synthetic leather is not necessarily limited, and may be a shape determined by the shape of the perforated projection, and a circle is particularly preferable. . The size of the aperture is preferably about 0.03 to 7 mm ² as the effective aperture area.
The opening ratio is preferably set to about 1 to 40% with respect to the synthetic leather area. If the effective aperture area is 0.03 mm ² or less, the aperture is too small to obtain deodorant properties, and if it exceeds 7 mm ² , the appearance of the synthetic leather is impaired. On the other hand, if the opening ratio is 1% or less, the number of openings is too small to obtain a deodorant property, and if it exceeds 40%, the strength of the synthetic leather decreases. As a device for forming openings on the surface of the synthetic leather, a heat roll having a large number of metallic needles arranged thereon and a receiving roll thereof can be used. It is preferable that the metallic needle is previously heated to a temperature of 80 to 200 ° C.

On the surface of the synthetic leather of the present invention, a surface treatment layer may be provided by a conventional gravure roll coater or the like, if necessary, within the range of the effective opening area and the opening ratio described above. You can also. The step of providing the surface treatment layer on the surface of the synthetic leather may be before or after the opening is formed in the synthetic leather. As the synthetic resin solution for forming the surface treatment layer, a polyamide resin solution, an acrylic resin solution, a polyamino acid resin solution, a silicone resin solution, and the like can be used in addition to the polyurethane resin solution described above. In addition, various additives as necessary also in the synthetic resin solution forming these surface treatment layers, for example,
Known additives such as a coloring agent, a crosslinking agent, a stabilizer, a natural powder, a filler and the like can be appropriately compounded.

[0029]

The synthetic leather of the present invention has excellent deodorant properties while being capable of being colored arbitrarily by including a deodorant in the polyurethane resin layer and providing openings through the synthetic leather. For example, it is useful as a material for shoes, gloves, bags, bags, furniture, vehicles, and the like used in places where a bad smell or a bad smell is generated or accumulated.

[0030]

EXAMPLES The present invention will be described in more detail with reference to specific examples below, but the present invention is not limited to the following examples. In the following description, “parts” or “%” is based on weight unless otherwise specified.

Example 1 A mixture of a polyurethane resin obtained by blending 100 parts of a polycarbonate-based polyurethane resin (solid content: 25%), 15 parts of a coloring agent, and 15 parts of dimethylformamide as a diluting solvent on a release paper with squeezing was used. 100 with knife coater
g / m ² · Wet, and dried by heating at 110 ° C. for 2 minutes to form a polyurethane resin film layer, which was used as a skin layer.

Next, manganese sulfate 1 was applied to the surface of the skin layer.
Mole and L-ascorbic acid 0.5 mole and citric acid 0.5
And 5 parts of a manganese (II) -organic acid compound and 100 parts of a polyether polyurethane resin (solid content 3
0%), 20 parts of a coloring agent, and 20 parts of dimethylformamide and 20 parts of methyl ethyl ketone as a diluting solvent. A polyurethane resin compounded liquid is applied by a knife coater in an amount of 110 g / m ² · Wet at 110 ° C. For 2 minutes to form a polyurethane resin film layer, which was used as a mesothelium layer.

Further, 100 parts of a two-component polyether-based polyurethane resin (solid content: 65%) was formed on the surface of the intermediate layer.
A polyurethane resin compounded liquid obtained by mixing 13 parts of a cross-linking agent, 5 parts of an accelerator, and 10 parts of dimethylformamide and 10 parts of toluene as a diluting solvent was subjected to 13 knife coating.
Coat in an amount of 0 g / m ² · Wet, pre-dry at 100 ° C. for 30 seconds, bond a brushed surface of a polyester tricot coarse brushed blank as a base material, heat dry at 120 ° C. for 3 minutes, and wind up Thereafter, the adhesive is cured by aging at 50 ° C. for 48 hours. Thereafter, the release paper was peeled off to obtain a synthetic leather suitable as a material for furniture.

The synthetic leather obtained as described above is needled from the base material side by a heating needle insertion device at a needle diameter of 1 mm, a needle pitch of 2 mm, and a needle temperature of 120 ° C. An opening having an opening rate of about 19% (effective opening area 0.79 mm ² ) was provided. The deodorizing effect of the obtained synthetic leather was measured by the following method. Table 1 shows the results.

[Deodorizing Test Method] (1) Ammonia: A sample (size: 180 × 250 mm, 1 sheet) was placed in a polyester film odor bag having a capacity of 3 liters, and 3 liters of clean air was placed in the odor bag containing the sample. And seal. 3.8 microliters of a 28% aqueous solution required to bring the initial concentration of ammonia in the odor bag to 500 ppm is collected in a microsyringe, injected into the odor bag and sealed. After complete gasification, it is stored at 25 ° C., and after 30 minutes and 60 minutes, the ammonia concentration is measured with a Kitagawa gas detector tube.

(2) Hydrogen Sulfide A sample (180 × 250 mm, 1 sheet) is put in a polyester film odor bag of 3 liter capacity, and 3 liters of clean air is put in the odor bag containing the sample and sealed. . 9.6 ml of 9.4% hydrogen sulfide gas required to bring the initial concentration of hydrogen sulfide in the odor bag to 300 ppm is collected in a gas tight syringe, injected into the odor bag and sealed. It is stored at 25 ° C., and after 30 minutes and 60 minutes, the concentration of hydrogen sulfide is measured with a Kitagawa gas detector tube.

(3) Trimethylamine A sample (180 × 250 mm, 1 sheet) is put in a 3 liter polyester film odor bag, and 3 liters of clean air is put in the odor bag containing the sample and sealed. 50ppm initial concentration of trimethylamine in odor bag
30% aqueous solution of trimethylamine required for
Microliters are collected in microsyringes, poured into odor bags and sealed. Store at 25 ° C, and after 30 minutes,
After 0 minute, the concentration of trimethylamine is measured with a gas-tech gas detector tube.

(4) Methyl mercaptan A sample (size: 180 × 250 mm, 1 sheet) is put in a 3 liter polyester film odor bag, and 3 liters of clean air is put in the odor bag containing the sample and sealed. . The initial concentration of methyl mercaptan in the odor bag was 100
Take 0.3 ml of methyl mercaptan gas required to obtain ppm in a gas tight syringe, inject into a smell bag and seal. After storing at 25 ° C., the methyl mercaptan concentration after 30 minutes and 60 minutes is measured with a Kitagawa gas detector tube.

Example 2 A polyester-based polyurethane resin 1 was placed on squeezed release paper.
A polyurethane resin blended liquid obtained by blending 00 parts (solid content 30%), 20 parts of a colorant, and 20 parts of dimethylformamide and 20 parts of methyl ethyl ketone as a diluting solvent in an amount of 120 g / m ² · Wet with a knife coater. Apply,
It was dried by heating at 110 ° C. for 3 minutes to form a polyurethane resin film layer, which was used as a skin layer.

Next, manganese sulfate 1 was applied to the surface of the skin layer.
Mol and 0.5 mol of L-ascorbic acid and 0.7 mol of citric acid
5 mol of manganese (II) -organic acid compound 1
0 parts and two-component polyester polyurethane resin 100
Parts (solid content 70%), a crosslinking agent 15 parts, an accelerator 5 parts, and a polyurethane resin compounded liquid obtained by mixing 10 parts of dimethylformamide and 10 parts of toluene as a diluting solvent with a knife coater at 120 g / m ^2. Apply in the amount of Wet, 1
Preliminarily dried at 00 ° C. for 30 seconds, and a polyester / polyamide non-woven fabric as a base material is stuck on the surface, and the temperature is reduced to 120 ° C.
After heating for 3 minutes, winding and aging at 50 ° C. for 48 hours to cure the adhesive. Thereafter, the release paper was peeled off to obtain a synthetic leather suitable as a material for shoe soles.

The synthetic leather obtained as described above was used with a needle diameter of 0.5 mm, a needle pitch of 1.5 mm, and a needle temperature of 130 mm.
The needle was inserted from the surface of the base material through a heating needle insertion device at a temperature of 0 ° C., and an opening having an opening ratio of about 9% (effective opening area 0.20 mm ² ) penetrating to the surface layer was provided. The deodorizing effect of the obtained synthetic leather was measured in the same manner as in Example 1. Table 1 shows the results.

Example 3 The procedure of Example 1 was repeated except that the manganese (II) -organic acid compound was replaced with a manganese (II) -organic acid compound obtained from 1 mol of manganese sulfate and 0.5 mol of L-ascorbic acid. Similarly, synthetic leather was obtained. The deodorizing effect of the obtained synthetic leather was measured in the same manner as in Example 1. Table 1 shows the results.

Example 4 Manganese (II)-Manganese (II) obtained by preparing an organic acid compound from 1 mol of manganese sulfate and 0.75 mol of citric acid.
Synthetic leather was obtained in the same manner as in Example 1 except that the organic acid compound was used. The deodorizing effect of the obtained synthetic leather was measured in the same manner as in Example 1. Table 1 shows the results
Shown in

Example 5 Synthetic leather was obtained in the same manner as in Example 1 except that activated carbon was added instead of the manganese (II) -organic acid compound. The deodorizing effect of the obtained synthetic leather was measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 A synthetic leather was obtained in the same manner as in Example 1 except that no manganese (II) -organic acid compound was added. The deodorizing effect of the obtained synthetic leather was measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 A synthetic leather was obtained in the same manner as in Example 2 except that no manganese (II) -organic acid compound was added. The deodorizing effect of the obtained synthetic leather was measured in the same manner as in Example 1. Table 1 shows the results.

[0047]

[Table 1]

[0048]

The synthetic leather of the present invention has an excellent deodorizing effect on many malodorous gases including four major malodorous components such as ammonia, trimethylamine, methyl mercaptan, hydrogen sulfide and the like over a long period of time. , Can be arbitrarily colored, and without discoloration to brown, clothing,
It can be particularly suitably used as a material for gloves, bags, bags, shoes, furniture, vehicles and the like.

Claims (4)

(57) [Claims] 1. A synthetic leather in which a single or a plurality of polyurethane resin coating layers are laminated on a fiber base material surface via a polyurethane resin adhesive layer, a polyurethane resin coating layer and a polyurethane resin adhesive layer which are not the outermost skin layer. Synthetic leather characterized in that at least one layer selected from the group consisting of a deodorant and a plurality of openings penetrating the synthetic leather. 2. The synthetic leather according to claim 1, wherein the deodorant is a compound obtained by binding at least one acid selected from ascorbic acid and oxypolybasic acid or a salt thereof to manganese (II) ions. . 3. The synthetic leather, wherein an opening penetrating through the synthetic leather has an effective opening area of 0.03 to 7 mm ² and an opening ratio of 1 to 40% with respect to the area of the synthetic leather. The synthetic leather according to claim 1. 4. A synthetic leather is formed by sequentially laminating a single layer or a plurality of polyurethane resin coating layers on the surface of a fiber base material such as a knitted fabric, a woven fabric, or a nonwoven fabric via a polyurethane resin adhesive layer. A method for producing synthetic leather in which a heated metallic needle is inserted from the back side of the synthetic leather to provide a plurality of through-holes in the surface of the synthetic leather, wherein the polyurethane resin coating layer and the polyurethane resin which are not the outermost skin layer A method for producing synthetic leather, wherein at least one layer selected from an adhesive layer contains a deodorant.