JP5090320B2 - Synthetic leather consisting of plant-derived components - Google Patents

Description

  The present invention relates to a synthetic leather (artificial leather), more specifically used for clothing, particularly for sports clothing that requires durability and breathability, such as gloves for golf and baseball batting. TECHNICAL FIELD The present invention relates to synthetic leather containing plant-derived components that contribute to carbon neutrality in order to reduce environmental burdens in global warming countermeasures.

  Polylactic acid resin is widely known as a resin composed of plant-derived components, and is characterized by biodegradability (for example, Patent Document 1).

  However, synthetic leather with good biodegradability is a concern that problems may occur in actual use in applications that require durability. The current general polylactic acid resin is difficult to maintain strength even in one week in a hydrolyzability evaluation test (70 ° C. × 95% RH), and is not used in applications that require durability. is there.

That is, the practical use of synthetic biodegradable leather using polylactic acid as a plant-derived component has not yet been realized.
JP 2002-20530 A

The present invention has been made in view of the above, and provides a synthetic leather capable of reducing the environmental load by solving the problem of durability against hydrolysis that cannot be solved only by plant-derived components such as polylactic acid resin. For the purpose.

  As a result of intensive studies, the present inventors have used a polyurethane resin containing 30 to 65% (% by weight, the same applies hereinafter) plant-derived components obtained by a coating method, a joining method, or an impregnation method on one side of a woven fabric, a knitted fabric, or a non-woven fabric. As a result, it was found that the above problems could be solved, and the present invention was completed.

That synthetic leather of the present invention, in order to solve the above problems, meet those polyurethane resin film containing a plant-derived component from 30 to 65% by weight, formed by formed by a coating method or a joining method on one surface of the fabric Then, a non-porous membrane containing 30 to 65% by weight of the plant-derived component formed by the skin-drawn process paper is transferred and laminated on the polyurethane porous membrane containing 30 to 65% by weight of the plant-derived component, and then By utilizing the difference in the thickness of the pore film, the pores are formed by re-dissolution by solvent coating to exhibit air permeability .

  As the polyol component constituting the polyurethane resin, castor oil diol is preferably used.

  The castor oil diol is a castor oil-based polyether polyester diol having an average number of hydroxyl groups of 1.8 to 2.1 and a hydroxyl value of 41 to 85 mgKOH / g.

  The synthetic leather of the present invention preferably has a durability that the retention of tensile strength after 3 weeks is 80% or more in a hydrolyzability evaluation test under conditions of a temperature of 70 ° C. and a humidity of 95%.

  The synthetic leather of the present invention has durability equivalent to or higher than that of products developed for each use such as furniture, clothing, footwear, sports gloves, etc., manufactured by a polyurethane resin comprising an existing petroleum component. It will be a thing. In addition, carbon neutrality through the use of plant-derived components contributes to the reduction of environmental burden as part of global warming prevention measures.

  In addition, by mainly using castor oil-based polyol as the polyol component of the polyurethane resin, durability which is a problem of plant-derived component resins having biodegradability such as polylactic acid resin can be improved and hydrolyzed. In the evaluation test (70 ° C. × 95% RH), durability equivalent to or higher than that of the polycarbonate-based polyurethane composed of petroleum components can be realized.

  As described above, the synthetic leather of the present invention has a polyurethane resin film containing a plant-derived component formed on one side by a coating method or a bonding method. Hereinafter, the present invention will be described in more detail.

1. Regarding Fabrics As the base material used in the synthetic leather of the present invention, those necessary according to the purpose of use and the like can be suitably used. Examples include synthetic fibers such as polyamide fibers (nylon fibers) and polyester fibers; Examples include semi-synthetic fibers such as fibers and rayon fibers; and natural fibers such as cotton and wool. These various fibers can be used alone or in admixture of two or more. Moreover, the structure is not particularly limited, and a woven fabric, a knitted fabric, a nonwoven fabric, or the like can be used as appropriate.

2. About polyurethane resin film As a polyurethane resin containing 30 to 65% by weight of plant-derived components, those synthesized mainly using plant-derived components such as divalent plant-derived polyols as polyol components can be suitably used.

  As the divalent plant-derived polyol, a castor oil diol can be suitably used because a polyurethane resin excellent in hydrolyzability can be obtained.

Castor oil is a triglyceride of ricinoleic acid represented mainly by the following formula:

Ricinoleic acid is a compound having a structure represented by the following formula.

  The castor oil diol as referred to in the present invention is a diol derived from castor oil, among which castor oil-based polyether polyester diol has an average number of hydroxyl groups of 1.8 to 2.1, and a hydroxyl value of 41 to 41. Those having 85 mg KOH / g are preferred, and those having an average number of hydroxyl groups of 1.95 to 2.05 can be suitably used. When the number of hydroxyl groups exceeds 2.1, it is difficult to obtain a polyurethane resin suitable for coating for forming a resin film because of the generation of a trivalent polyol branch or crosslinked structure. That is, it is preferable that the urethane resin used in the present invention has a linear structure, has little branching or cross-linking structure, and has a solution viscosity that can be coated on a fabric. Increasing the branch structure increases the viscosity and makes it unsuitable for coating. Moreover, when it becomes a crosslinked structure, the viscosity change occurs even in a very small amount, the viscosity change is large even in a small amount, and if the amount of crosslinking further increases, a urethane resin solution cannot be obtained.

  The proportion of the plant-derived component in the polyurethane resin is preferably larger from the viewpoint of reducing the environmental load, but in order to improve the performance of the polyurethane resin film and obtain the synthetic leather targeted by the present invention, the lower limit is 30. % By weight and the upper limit is 65% by weight.

3. Characteristics and production method of synthetic leather The synthetic leather of the present invention preferably has a tensile strength retention of 80% or more after 3 weeks in a hydrolyzability evaluation test under a 95% humidity condition.

  In the present invention, by using the polyether polyester polyol derived from castor oil as the divalent polyol which is a raw material of polyurethane as described above, the hydrolytic evaluation test for the tensile strength of synthetic leather after 3 weeks has passed. It is possible to set the retention rate at 80% or more. Further, even after 15 weeks, a highly durable synthetic leather having a tensile strength retention of 50% or more, which is 5 times or more of that obtained using a normal polyester polyol, can be obtained.

  Examples of a method for obtaining a polyurethane resin containing plant-derived components include polar solvents such as dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and solvents such as methyl ethyl ketone (MEK), toluene, and xylene. In addition, a divalent plant-derived polyol such as castor oil diol is dissolved, and here a divalent isocyanate (hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate: MDI, hydrogenated MDI, etc.) is added and reacted sufficiently. After preparing a prepolymer having an isocyanate or a hydroxyl group at the terminal, a diol (petroleum-derived ethylene glycol, propylene glycol, butylene glycol, etc., plant-derived 1,3-propanediol, 1,2-hexanediol, etc. ), Or a divalent isocyanate was added (hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate (MDI), and hydrogenated MDI), it is possible to use a method of increasing the polymerization degree of a chain extending reaction. However, the synthesis method of the polyurethane resin used in the present invention is not limited to the above method.

  In the above, when a prepolymer is formed by reacting a divalent plant-derived polyol and a divalent isocyanate, if necessary, in addition to the divalent plant-derived polyol, other polyols such as polyesters are used. It is also possible to copolymerize polyols and polyether polyols. More specifically, divalent petroleum-derived polyols such as polyethylene adipate, polybutylene adipate, polycaprolactone diol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can be copolymerized. Alternatively, polycarbonate polyol, silicone polyol, fluorine polyol, polyamide polyol and the like can be copolymerized and used. Polyols other than these plant-derived polyols can be mixed in a proportion of 50% by weight (solid content ratio) or less in the total amount of polyol, but the mixing amount is 25% by weight (solid content ratio) in order not to reduce the plant-derived ratio. The following is desirable.

  Regarding the method for producing the synthetic leather of the present invention, as a method of laminating a polyurethane resin film containing a plant-derived component on a fabric, there are a method of coating the fabric directly (coating method) and a method of impregnation by dipping. .

  In the coating method, various coating methods such as knife coating, knife over roll coating, and reverse roll coating can be used.

  In addition, as a bonding method, for example, a method of peeling a release paper after laminating a polyurethane resin film formed on a release paper by coating or the like with a dot or a whole surface with an adhesive is used, but is not limited thereto.

  As an example of a preferable embodiment for forming a porous film, a polyurethane resin solution obtained by dissolving a polyurethane resin containing a plant-derived component in a polar solvent (DMF, DMSO, etc.) soluble in water is coated on a substrate. And a method of forming a porous film by wet-gelling in water or an aqueous solution containing a polar solvent.

  When laminating a non-porous film on a porous film, the non-porous film of the surface layer is formed by coating the release paper with a polyurethane resin solution and drying the solvent, and then bonding the entire surface with an adhesive, Although there is a method of peeling the release paper after laminating on the substrate after forming the porous layer in a semi-dry state at the time of forming the porous film, it is not limited thereto.

  As an example of a preferred embodiment, a non-porous film formed by a process paper with skin-squeezing is transferred and laminated on a porous film, and then, by utilizing the difference in thickness of the non-porous film, re-dissolution by solvent coating is used to form a hole. Thus, air permeability can be expressed. For example, by applying a solvent to the surface with a gravure coater, due to the film thickness difference of the ridges and valleys of the handle, the valley portion is dissolved and at the same time the intermediate surface is dissolved, resulting in continuous holes formed by a wet process. Breathability is expressed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by the following examples. In addition, the following were used as a measuring method of various performance in this-application specification etc. including a following example. Moreover,% is weight%.

(Measuring method)
(1) Jungle test: hydrolysis was promoted in a high-temperature constant temperature bath at 70 ° C. and a relative humidity of 95%, and the ratio (%) of the tensile strength after the test to the tensile strength before the test was examined.

(2) Tensile strength measurement: Measured at a rate of 100 mm / min with an STA-1225 tensile tester manufactured by Orientec.

(3) Wear strength measurement: Taber type abrasion tester manufactured by Daiei Chemical Seiki Seisakusho Co., Ltd., CS-10 manufactured by US Taber Co., Ltd. was used as a wear wheel, and the grade was determined under test conditions of 1 kg load × 2000 times (5 stages). Went.

(4) Boiling test with 5% NaOH aqueous solution: A stainless steel vat is immersed in a boiling (approximately 100 ° C.) state with an electromagnetic induction heater to observe the dissolution of the film, and the time course is evaluated in minutes. did.

(5) Air permeability measurement: Measured using a Fragile air permeability test AP-360 manufactured by Daiei Seiki Co., Ltd.

<Plant-derived polyurethane resin 30% solution 1>
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) and 76.8 g of castor oil diol 2 (manufactured by Ito Oil Co., Ltd., H- 56, average hydroxyl group number: 2.03, hydroxyl value: 83 mg KOH / g) 19.2 g, polybutylene adipate (manufactured by Nippon Polyurethane Co., Ltd., BA-2000) 4 g and dimethylformamide (hereinafter abbreviated as DMF) 121 g was dissolved in 1 liter of separable colben, 41.7 g of MDI was added while adjusting the temperature to 45 ° C., and the mixture was reacted at 45 ° C. for about 1 hour to obtain a prepolymer. Thereafter, the temperature was raised to 60 ° C., 10.8 g of 1,4-butylene glycol was added, a chain length extension reaction was carried out at 60 ° C., and polymerization was carried out while adding 235 g of DMF in proportion to the increase in viscosity. Polymerization was completed in about 8 hours, and a 30% polyurethane resin solution having a plant-derived rate of 63% (solid content ratio) was obtained.

<Plant-derived polyurethane resin 30% solution 2>
Castor oil diol 1 (produced by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) and castor oil diol 2 (produced by Ito Oil Co., Ltd., H-56, 1 liter of average hydroxyl number: 2.03, hydroxyl value: 83 mg KOH / g) 48 g, polybutylene adipate (Nippon Polyurethane Co., Ltd., BA-2000) 20 g and dimethylformamide (hereinafter abbreviated as DMF) 139 g Was dissolved in separable colben, and 52.7 g of MDI was added while adjusting the temperature to 45 ° C., and the mixture was allowed to react at 45 ° C. for approximately 1 hour to obtain a prepolymer. Thereafter, the temperature was raised to 60 ° C., 13.9 g of 1,4-butylene glycol was added, a chain length extension reaction was carried out at 60 ° C., and polymerization was carried out while 250 g of DMF was added in portions as the viscosity increased. The polymerization was completed in about 8 hours, and a 30% polyurethane resin solution having a plant-derived ratio of 48% (solid content ratio) was obtained.

<Plant-derived polyurethane resin 30% solution 3>
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mgKOH / g) 42 g and castor oil diol 2 (manufactured by Ito Oil Co., Ltd., H-56, Average number of hydroxyl groups: 2.03, hydroxyl value: 83 mg KOH / g) 28 g, polybutylene adipate (manufactured by Nippon Polyurethane Co., Ltd., BA-2000) 30 g and DMF 140 g were dissolved in 1 liter separable colben, While adjusting the temperature to 45 ° C., 52 g of MDI was added and reacted at 45 ° C. for approximately 1 hour to obtain a prepolymer. Thereafter, the temperature was raised to 60 ° C., 14 g of 1,4-butylene glycol was added, a chain extension reaction was carried out at 60 ° C., and polymerization was carried out while adding 247 g of DMF in portions as the viscosity increased. Polymerization was completed in about 8 hours, and a 30% polyurethane resin solution having a plant-derived rate of 42.2% (solid content ratio) was obtained.

<Plant-derived polyurethane resin 30% solution 4>
Castor oil diol 1 (produced by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) and castor oil diol 2 (produced by Ito Oil Co., Ltd., H-56) Average number of hydroxyl groups: 2.03, hydroxyl value: 83 mg KOH / g) 36 g, polybutylene adipate (manufactured by Nippon Polyurethane Co., Ltd., BA-2000) 40 g and DMF 140 g were dissolved in 1 liter separable colben, While adjusting the temperature to 45 ° C., 51.2 g of MDI was added and reacted at 45 ° C. for approximately 1 hour to obtain a prepolymer. Thereafter, the temperature was raised to 60 ° C., 13.5 g of 1,4-butylene glycol was added, a chain extension reaction was carried out at 60 ° C., and polymerization was carried out while adding 244 g of DMF in portions as the viscosity increased. The polymerization was completed in about 8 hours, and a 30% polyurethane resin solution having a plant-derived ratio of 36.4% (ratio in solid content) was obtained.

<Plant-derived polyurethane resin 30% solution 5>
Castor oil diol 1 (Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) and castor oil diol 2 (Ito Oil Co., Ltd., H-56, Average number of hydroxyl groups: 2.03, hydroxyl value: 83 mg KOH / g) 30 g, polybutylene adipate (manufactured by Nippon Polyurethane Co., Ltd., BA-2000) 50 g and DMF 140 g were dissolved in 1 liter separable colben, While adjusting the temperature to 45 ° C., 50.5 g of MDI was added and reacted at 45 ° C. for approximately 1 hour to obtain a prepolymer. Thereafter, the temperature was raised to 60 ° C., 13.3 g of 1,4-butylene glycol was added, a chain extension reaction was carried out at 60 ° C., and polymerization was carried out while adding 242 g of DMF in proportion to the increase in viscosity. Polymerization was completed in about 8 hours, and a 30% polyurethane resin solution having a plant-derived rate of 30.5% (solid content ratio) was obtained.

<30% solution of petroleum-derived polyurethane resin>
100 g of polybutylene adipate (manufactured by Nippon Polyurethane Co., Ltd., BA-2000) and 144 g of DMF are dissolved in 1 liter of separable colben, and 46.9 g of MDI is added while adjusting the temperature to 45 ° C. It was made to react at 0 degreeC and was set as the prepolymer. Thereafter, the temperature was raised to 60 ° C., 12.4 g of 1,4-butylene glycol was added, a chain extension reaction was carried out at 60 ° C., and polymerization was carried out while adding 278 g of DMF in proportion to the increase in viscosity. Polymerization was completed in about 8 hours, and a 30% polyurethane resin solution having a petroleum-derived ratio of 100% (solid content ratio) was obtained.

[Example 1]
Nylon tricot treated with single-sided brushing as the base material (density: 42 wells / in course 54 / in, front 50 denier / 48 filament, back 30 denier / 10 filament warp half tricot) For the purpose of imparting dimensional stability, a composite material was used in which a woven fabric of rayon material (number of driven-in 90 yarns / in) was laminated on the surface opposite to the raised surface with an acrylic / vinyl acetate emulsion resin as a binder.

  As a pretreatment for coating, the base material was immersed in water, and the mangle was adjusted so that 80 to 90% of water adhered to the base material weight.

  Next, <plant-derived polyurethane resin 30% solution 1> 100.0 parts by weight, DMF 120 parts by weight, anionic surfactant (Dai Kogyo Seiyaku Co., Ltd., Neocor (registered trademark) SW-C) 3.0 parts by weight Parts, nonionic additives (Dainippon Ink Chemical Co., Ltd., Crisbon (registered trademark) Asister SD-7) 2.0 parts by weight, pigments (Dainippon Ink Chemical Co., Ltd., Dilack (registered trademark) L-7560) 20.0 parts by weight were added and stirred to obtain a polyurethane blend solution having a plant-derived rate of 61.8% (solid content ratio).

The pre-treated base material is coated with a knife over roll coater at a coating amount of 800 g / m ² , and immersed in an aqueous solution containing 10% by weight of DMF in a coagulation bath at 30 ° C. for 10 minutes to obtain a polyurethane resin compounded solution. Precipitated and solidified, then immersed and washed in hot water at 80 ° C. for 30 minutes and dried with hot air at 120 ° C. to obtain an intermediate having a plant-derived rate of 61.8% (ratio in the solid content of the laminated resin layer) It was.

  Next, <plant-derived polyurethane resin 30% solution 1> 100.0 parts by weight, solvent methyl ethyl ketone 120 parts by weight, acrylic silicone (manufactured by Shin-Etsu Silicone Co., Ltd., KP-366), 2 parts by weight, pigment (Daiichi Seika Kogyo Co., Ltd.) ), BS-780) 30 parts by weight was added and stirred to obtain a polyurethane resin blending liquid having a plant-derived rate of 48.8% (solid content ratio).

Next, coating on process paper (Dai Nippon Printing Co., Ltd., DE-43) at a coating amount of 40 g / m ^{2 with} a knife over roll coater, pre-drying with a dryer at 70 ° C. for 30 seconds, and compounding with resin In the semi-dried state where the solvent of the liquid remained, it was bonded to the resin surface of the intermediate prepared previously, and the intermediate surface was integrated by dissolving with the residual solvent, and dried with hot air at 140 ° C. As a result, a non-porous film having a thickness of 6 μm was formed on the intermediate.

  A sheet material with a leather-like pattern transferred was obtained by peeling the process paper.

Next, the solvent DMF is applied to the surface with a roll engraved to 150 mesh with a gravure coater at a coating amount of 15 g / m ² , so that the valley portion of the ridge and valley and the intermediate surface are dissolved. Breathability was expressed by the formed continuous holes.

  And the synthetic leather of the plant origin rate 61.1% (ratio in solid content of laminated resin) was obtained by peeling the rayon fabric used as a reinforcing material. The evaluation results are shown in Table 1.

[Example 2]
Nylon tricot treated with single-side raised as a base material (density: 42 wells / in course 54 / in, front 50 denier / 48 filament, back 30 denier / 10 filament warp knitted half tricot) For the purpose of imparting dimensional stability, a composite material was used in which a woven fabric of rayon material (number of driven-in 90 yarns / in) was laminated on the surface opposite to the raised surface with an acrylic / vinyl acetate emulsion resin as a binder.

  As a pretreatment for coating, the base material was immersed in water, and the mangle was adjusted so that 80 to 90% of water adhered to the base material weight.

  Next, <plant-derived polyurethane resin 30% solution 2> 100.0 parts by weight, DMF 120 parts by weight, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neocor (registered trademark) SW-C) 3.0 parts by weight Parts, nonionic additives (Dainippon Ink Chemical Co., Ltd., Crisbon (registered trademark) Asister SD-7) 2.0 parts by weight, pigments (Dainippon Ink Chemical Co., Ltd., Dilack (registered trademark) L-7560) 20.0 parts by weight were added and stirred to obtain a polyurethane blend solution having a plant-derived rate of 47.1% (solid content ratio).

The pre-treated base material is coated with a knife over roll coater at a coating amount of 800 g / m ² , and immersed in an aqueous solution containing 10% by weight of DMF in a coagulation bath at 30 ° C. for 10 minutes to obtain a polyurethane resin compounded solution. Precipitated and solidified, then immersed and washed in hot water at 80 ° C. for 30 minutes and dried with hot air at 120 ° C. to obtain an intermediate having a plant-derived rate of 47.1% (ratio in solid content of the laminated resin layer) It was.

  Next, <plant-derived polyurethane resin 30% solution 2> 100.0 parts by weight, solvent methyl ethyl ketone 120 parts by weight, acrylic silicone (manufactured by Shin-Etsu Silicone Co., Ltd., KP-366), 2 parts by weight, pigment (Daiichi Seika Kogyo Co., Ltd.) ), BS-780) 30 parts by weight were added and stirred to obtain a polyurethane resin blending liquid with a plant-derived rate of 37.9% (solid content ratio).

Next, coating on process paper (Dai Nippon Printing Co., Ltd., DE-43) at a coating amount of 40 g / m ^{2 with} a knife over roll coater, pre-drying with a dryer at 70 ° C. for 30 seconds, and compounding with resin In the semi-dried state where the solvent of the liquid remained, it was bonded to the resin surface of the intermediate prepared previously, and the intermediate surface was integrated by dissolving with the residual solvent, and dried with hot air at 140 ° C. As a result, a non-porous film having a thickness of 6 μm was formed on the intermediate.

  A sheet material with a leather-like pattern transferred was obtained by peeling the process paper.

Next, the solvent DMF is applied to the surface with a roll engraved to 150 mesh with a gravure coater at a coating amount of 15 g / m ² , so that the valley portion of the ridge and valley and the intermediate surface are dissolved. Breathability was expressed by the formed continuous holes.

  Then, by peeling off the rayon fabric as a reinforcing material, a synthetic leather having a plant-derived rate of 46.6% (ratio in the solid content of the laminated resin) was obtained. The evaluation results are shown in Table 1.

[Example 3]
Nylon tricot treated with single-side raised as a base material (density: 42 wells / in course 54 / in, front 50 denier / 48 filament, back 30 denier / 10 filament warp knitted half tricot) For the purpose of imparting dimensional stability, a composite material was used in which a woven fabric of rayon material (number of driven-in 90 yarns / in) was laminated on the surface opposite to the raised surface with an acrylic / vinyl acetate emulsion resin as a binder.

  As a pretreatment for coating, the base material was immersed in water, and the mangle was adjusted so that 80 to 90% of water adhered to the base material weight.

  Next <plant-derived polyurethane resin 30% solution 3> 100.0 parts by weight DMF: 120 parts by weight, anionic surfactant (Dai Kogyo Seiyaku Co., Ltd., Neocor (registered trademark) SW-C) 3.0 Parts by weight, 2.0 parts by weight of nonionic additives (Dainippon Ink Chemical Co., Ltd., Crisbon (registered trademark) Asister SD-7), pigments (Dainippon Ink Chemical Co., Ltd., Dilack (registered trademark) ) L-7560) 20.0 parts by weight were added and stirred to obtain a polyurethane blend solution with a plant-derived rate of 41.4% (solid content ratio).

A pretreated substrate is coated with a knife over roll coater at a coating amount of 800 g / m ² , and immersed in an aqueous solution containing 10% by weight of DMF in a coagulation bath at 30 ° C. for 10 minutes for blending with polyurethane resin The solution was precipitated and solidified, then immersed and washed in hot water at 80 ° C. for 30 minutes, dried with hot air at 120 ° C., and an intermediate having a plant-derived rate of 41.4% (ratio in the solid content of the laminated resin layer) Got.

  Next, <plant-derived polyurethane resin 30% solution 3> 100.0 parts by weight, solvent methyl ethyl ketone: 120 parts by weight, acrylic silicone (manufactured by Shin-Etsu Silicone Co., Ltd., KP-366), 2 parts by weight, pigment (Daiichi Seikagaku ( Co., Ltd., BS-780) 30 parts by weight was added and stirred to obtain a polyurethane resin blend liquid having a plant-derived rate of 33.3% (solid content ratio).

Next, coating on process paper (Dai Nippon Printing Co., Ltd., DE-43) at a coating amount of 40 g / m ^{2 with} a knife over roll coater, pre-drying with a dryer at 70 ° C. for 30 seconds, and compounding with resin In the semi-dried state where the solvent of the liquid remained, it was bonded to the resin surface of the intermediate prepared previously, and the intermediate surface was integrated by dissolving with the residual solvent, and dried with hot air at 140 ° C. As a result, a non-porous film having a thickness of 6 μm was formed on the intermediate.

  A sheet material with a leather-like pattern transferred was obtained by peeling the process paper.

Next, 15 g / m ² of solvent DMF was applied to the surface with a roll engraved with 150 mesh by a gravure coater. As a result, the valley portions of the struts and the intermediate surface were dissolved, and air permeability was expressed by the continuous holes formed by the wet manufacturing method.

  And the synthetic leather of 41.0% of plant origin ratio (ratio in solid content of laminated resin) was obtained by peeling the rayon fabric used as a reinforcing material. The evaluation results are shown in Table 1.

[Example 4]
Nylon tricot with brushed surface as the base material (density: 42 wells / in course 54 / in, front 50 denier / 48 filament, back 30 denier / 10 filament warp knitted half tricot) For the purpose of imparting dimensional stability, a composite material obtained by laminating a woven fabric of rayon material (number of driven-in 90 yarns / in) on the surface opposite to the raised surface with an acrylic / vinyl acetate emulsion resin as a binder was used.

  As a pretreatment for coating, the base material was immersed in water, and the mangle was adjusted so that 80 to 90% of water adhered to the base material weight.

  Next, <plant-derived polyurethane resin 30% solution 4> 100.0 parts by weight, DMF 120 parts by weight, an anionic surfactant (Dai Kogyo Seiyaku Co., Ltd., Neocor (registered trademark) SW-C) 3.0 parts by weight Parts, nonionic additives (Dainippon Ink Chemical Co., Ltd., Crisbon (registered trademark) Asister SD-7) 2.0 parts by weight, pigments (Dainippon Ink Chemical Co., Ltd., Dilack (registered trademark) L-7560) 20.0 parts by weight were added and stirred to obtain a polyurethane blending solution having a plant-derived rate of 35.7% (solid content ratio).

The pre-treated base material is coated with a knife over roll coater at a coating amount of 800 g / m ² , and immersed in an aqueous solution containing 10% by weight of DMF in a coagulation bath at 30 ° C. for 10 minutes to obtain a polyurethane resin compounded solution. It was precipitated and solidified, then immersed and washed in hot water at 80 ° C. for 30 minutes, and dried with hot air at 120 ° C. to obtain an intermediate having a plant-derived ratio of 35.7% (ratio in the solid content of the laminated resin layer).

  Next, <plant-derived polyurethane resin 30% solution 4> 100.0 parts by weight, solvent methyl ethyl ketone 120 parts by weight, acrylic silicone (manufactured by Shin-Etsu Silicone Co., Ltd., KP-366), 2 parts by weight, pigment (Daiichi Seika Kogyo Co., Ltd.) ), BS-780) 30 parts by weight were added and stirred to obtain a polyurethane resin blend liquid having a plant-derived rate of 28.7% (solid content ratio).

Next, coating on process paper (Dai Nippon Printing Co., Ltd., DE-43) at a coating amount of 40 g / m ^{2 with} a knife over roll coater, pre-drying with a dryer at 70 ° C. for 30 seconds, and compounding with resin In the semi-dried state where the solvent of the liquid remained, it was bonded to the resin surface of the intermediate prepared previously, and the intermediate surface was integrated by dissolving with the residual solvent, and dried with hot air at 140 ° C. As a result, a non-porous film having a thickness of 6 μm was formed on the intermediate.

  A sheet material with a leather-like pattern transferred was obtained by peeling the process paper.

Next, the solvent DMF is applied to the surface with a roll engraved to 150 mesh with a gravure coater at a coating amount of 15 g / m ² , so that the valley portion of the ridge and valley and the intermediate surface are dissolved. Breathability was expressed by the formed continuous holes.

  Then, by peeling off the rayon fabric as a reinforcing material, a synthetic leather having a plant-derived rate of 35.3% (ratio in the solid content of the laminated resin) was obtained. The evaluation results are shown in Table 1.

[Example 5]
Nylon tricot treated with single-side raised as a base material (density: 42 wells / in course 54 / in, front 50 denier / 48 filament, back 30 denier / 10 filament warp knitted half tricot) For the purpose of imparting dimensional stability, a composite material was used in which a woven fabric of rayon material (number of driven-in 90 yarns / in) was laminated on the surface opposite to the raised surface with an acrylic / vinyl acetate emulsion resin as a binder.

  As a pretreatment for coating, the base material was immersed in water, and the mangle was adjusted so that 80 to 90% of water adhered to the base material weight.

  Next <plant-derived polyurethane resin 30% solution 5> 100.0 parts by weight DMF 120 parts by weight, anionic surfactant (Dai Kogyo Seiyaku Co., Ltd., Neocor (registered trademark) SW-C) 3.0 parts by weight , 2.0 parts by weight of a nonionic additive (Dainippon Ink Chemical Co., Ltd., Crisbon (registered trademark) Asister SD-7), Pigment (Dailac Ink Chemical Co., Ltd., Dilack (registered trademark) L) -7560) 20.0 parts by weight were added and stirred to obtain a polyurethane blending solution having a plant-derived rate of 47.1% (solid content ratio).

The pre-treated base material is coated with a knife over roll coater at a coating amount of 800 g / m ² , and immersed in an aqueous solution containing 10% by weight of DMF in a coagulation bath at 30 ° C. for 10 minutes to obtain a polyurethane resin compounded solution. Precipitated and solidified, then immersed and washed in hot water at 80 ° C. for 30 minutes and dried in hot air at 120 ° C. to obtain an intermediate having a plant-derived rate of 29.9% (ratio in the solid content of the laminated resin layer).

  Next, <plant-derived polyurethane resin 30% solution 5> 100.0 parts by weight, solvent methyl ethyl ketone 120 parts by weight, acrylic silicone (manufactured by Shin-Etsu Silicone Co., Ltd., KP-366), 2 parts by weight, pigment (Daiichi Seika Kogyo Co., Ltd.) ), BS-780) 30 parts by weight were added and stirred to obtain a polyurethane resin blend liquid having a plant-derived rate of 24.1% (solid content ratio).

Next, coating on process paper (Dai Nippon Printing Co., Ltd., DE-43) at a coating amount of 40 g / m ^{2 with} a knife over roll coater, pre-drying with a dryer at 70 ° C. for 30 seconds, and compounding with resin In the semi-dried state where the solvent of the liquid remained, it was bonded to the resin surface of the intermediate prepared previously, and the intermediate surface was integrated by dissolving with the residual solvent, and dried with 140 ° C. hot air. As a result, a non-porous film having a thickness of 6 μm was formed on the intermediate.

  A sheet material with a leather-like pattern transferred was obtained by peeling the process paper.

Next, the solvent DMF was applied to the surface at a coating amount of 15 g / m ² with a roll engraved to 150 mesh with a gravure coater. As a result, the valley portions of the struts and the intermediate surface were dissolved, and air permeability was expressed by the continuous holes formed by the wet manufacturing method.

  And the synthetic leather of 29.6% of plant origin ratio (ratio in solid content of laminated resin) was obtained by peeling the rayon fabric used as a reinforcing material. The evaluation results are shown in Table 1.

[Comparative example]
Nylon tricot with brushed surface as the base material (density: 42 wells / in course 54 / in, front 50 denier / 48 filament, back 30 denier / 10 filament warp knitted half tricot) For the purpose of imparting dimensional stability, a composite material obtained by laminating a woven fabric of rayon material (number of driven-in 90 yarns / in) on the surface opposite to the raised surface with an acrylic / vinyl acetate emulsion resin as a binder was used.

  As a pretreatment for coating, the base material was immersed in water, and the mangle was adjusted so that 80 to 90% of water adhered to the base material weight.

  Next, <30% petroleum-derived polyurethane resin solution> 100.0 parts by weight, DMF 120 parts by weight, anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neocor (registered trademark) SW-C) 3.0 parts by weight , 2.0 parts by weight of a nonionic additive (Dainippon Ink Chemical Co., Ltd., Crisbon (registered trademark) Asister SD-7), Pigment (Dailac Ink Chemical Co., Ltd., Dilack (registered trademark) L) -7560) 20.0 parts by weight were added and stirred to obtain a polyurethane blending solution having a petroleum-derived rate of 100% (ratio in solid content).

A pretreated substrate is coated with a knife over roll coater at a coating amount of 800 g / m ² , and immersed in an aqueous solution containing 10% by weight of DMF in a coagulation bath at 30 ° C. for 10 minutes for blending with polyurethane resin The liquid was precipitated and solidified, then immersed and washed in hot water at 80 ° C. for 30 minutes, and dried with hot air at 120 ° C. to obtain an intermediate having a petroleum-derived rate of 100% (ratio in the solid content of the laminated resin layer).

  Next, <30% petroleum-derived polyurethane resin solution> 100.0 parts by weight, solvent methyl ethyl ketone 120 parts by weight, acrylic silicone (manufactured by Shin-Etsu Silicone Co., Ltd., KP-366), 2 parts by weight, pigment (Daiichi Seika Kogyo Co., Ltd.) (Manufactured, BS-780) 30 parts by weight were added and stirred to obtain a polyurethane resin blending liquid having a petroleum-derived rate of 100% (solid content ratio).

Next, coating on process paper (Dai Nippon Printing Co., Ltd., DE-43) at a coating amount of 40 g / m ^{2 with} a knife over roll coater, pre-drying with a dryer at 70 ° C. for 30 seconds, and compounding with resin In the semi-dried state where the solvent of the liquid remained, it was bonded to the resin surface of the intermediate prepared previously, and the intermediate surface was integrated by dissolving with the residual solvent, and dried with hot air at 140 ° C. As a result, a non-porous film having a thickness of 6 μm was formed on the intermediate.

  A sheet material with a leather-like pattern transferred was obtained by peeling the process paper.

Next, 15 g / m ² of solvent DMF was applied to the surface with a roll engraved with 150 mesh with a gravure coater to dissolve the valley portion of the striking valley and the intermediate surface, and was formed by a wet manufacturing method. Breathability was expressed by the continuous holes.

  And the synthetic leather was obtained by peeling the rayon fabric used as the reinforcing material. The results are shown in Table 1.

  The synthetic leather of the present invention solves the problems of durability of conventional biodegradable plant-derived component resins such as polylactic acid resin, and has excellent breathability. Therefore, sports gloves such as golf and batting, and general clothing Etc. can be used suitably.

Claims (4)

A polyurethane resin film containing 30 to 65% by weight of a plant-derived component is a synthetic leather formed on one side of a fabric by a coating method or a joining method ,
A non-porous membrane containing 30 to 65% by weight of a plant-derived component formed by skin-drawn process paper is transferred and laminated to a polyurethane porous membrane containing 30 to 65% by weight of a plant-derived component, and then the non-porous membrane A synthetic leather characterized in that, by utilizing the difference in thickness, pores are formed by re-dissolution by solvent coating to exhibit air permeability. The synthetic leather according to claim 1 , wherein castor oil diol is used as a polyol component constituting a polyurethane resin containing 30 to 65% of the plant-derived component. The castor oil diol is a castor oil-based polyether polyester diol, the average number of hydroxyl groups is 1.8 to 2.1 units, and wherein the hydroxyl value is 41~85mgKOH / g, according to claim 2 Synthetic leather described in 1. The tensile strength retention after three weeks in a hydrolyzability evaluation test under conditions of a temperature of 70 ° C and a humidity of 95% is 80% or more, according to any one of claims 1 to 3. Synthetic leather as described.