JP2019065426A - Synthetic leather with excellent durability and antifouling performance - Google Patents

Abstract

【the purpose】
An object of this invention is to provide the synthetic leather which has the antifouling performance excellent in durability.
【Constitution】
The synthetic leather of the present invention is a synthetic leather laminated in the order of at least a fiber fabric substrate, a resin layer and a surface treatment layer, and the surface treatment layer of the synthetic leather has a measurement value of 60 dyne / cm or more by a wetting reagent. Measured by the wetting reagent of the surface treatment layer after performing each of 1) abrasion resistance test, 2) heat resistance test, and 3) light resistance test shown below show 50 dyne / cm or more. Synthetic leather with antifouling performance.
1) Wear resistance test: In a flat wear machine, set # 9 canvas on the friction element, apply a load so that the load pressure applied to the test piece is 2 Mpa, and reciprocate 20,000 times.
2) Heat resistance test: The test piece is placed in a gear oven and left to stand at a temperature of 100 ° C. for 500 hours for heat treatment.
3) Light resistance test: The test piece is treated with a fade meter tester at a temperature of 83 ° C. for 500 hours.
[Selected figure] None

Description

  The present invention relates to a synthetic leather having an antifouling performance excellent in durability.

  Synthetic leather has been used, for example, for car interior materials, furniture applications such as sofas, and clothing applications such as coats.

However, when dirt adheres to the surface of synthetic leather, it has been difficult to wipe the dirt clean. Therefore, particularly in the case of synthetic leather using a light-colored pigment in the surface layer, there is a problem that the stains become noticeable.
In particular, with regard to vehicle interior materials, adhesion of dirt and dirt is frequently observed, and there is a problem that dirt and dirt attached to synthetic leather are difficult to wipe off.

  As a countermeasure, as described in Patent Document 1, by forming a coating film in which a coating agent having antifouling performance is applied to the surface of synthetic leather, it is possible to easily wipe off even if dirt adheres. Is disclosed.

JP 2007-191820 A

However, for example, as in car interior materials, antifouling provided on the surface of synthetic leather due to wear deterioration due to load at the time of getting in and out, heat deterioration due to the rise of the temperature inside the car during summer or ultraviolet light deterioration due to sunlight The coating film having performance may deteriorate with time.
As a result, there has been a problem that the original antifouling performance, that is, the performance capable of being wiped clean even if, for example, dirt is attached, is not exhibited for a long time.

  Therefore, this invention aims at solving the said subject and providing the synthetic leather which has the antifouling performance excellent in durability.

  MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject, and invented the synthetic leather which has the antifouling performance excellent in following durability.

The synthetic leather of the present invention is a synthetic leather laminated in the order of at least a fiber fabric substrate, a resin layer and a surface treatment layer, and the surface treatment layer of the synthetic leather has a measurement value of 60 dyne / cm or more by a wetting reagent. Measured by the wetting reagent of the surface treatment layer after performing each of 1) abrasion resistance test, 2) heat resistance test, and 3) light resistance test shown below show 50 dyne / cm or more. Synthetic leather with antifouling performance.
1) Wear resistance test: In a flat wear machine, set # 9 canvas on the friction element, apply a load so that the load pressure applied to the test piece is 2 Mpa, and reciprocate 20,000 times.
2) Heat resistance test: The test piece is placed in a gear oven and left to stand at a temperature of 100 ° C. for 500 hours for heat treatment.
3) Light resistance test: The test piece is treated with a fade meter tester at a temperature of 83 ° C. for 500 hours.

  The synthetic leather having antifouling performance with excellent durability according to the present invention is, for example, wear deterioration due to the load when getting on and off, thermal deterioration due to the rise of the temperature inside the car such as midsummer, or solar light It is possible to suppress the deterioration of the antifouling performance with time due to a factor such as the deterioration of ultraviolet rays, and maintain the antifouling performance for a long time.

The synthetic leather of the present invention is a synthetic leather laminated in the order of at least a fiber fabric substrate, a resin layer and a surface treatment layer, and the surface treatment layer of the synthetic leather has a measurement value of 60 dyne / cm or more by a wetting reagent. Measured by the wetting reagent of the surface treatment layer after performing each of 1) abrasion resistance test, 2) heat resistance test, and 3) light resistance test shown below show 50 dyne / cm or more. Antifouling performance.
1) Wear resistance test: In a flat wear machine, set the No. 9 canvas on the friction element, apply a load so that the load pressure applied to the test piece is 2 Mpa, and reciprocate 20,000 times.
2) Heat resistance test: The test piece is placed in a gear oven and left to stand at a temperature of 100 ° C. for 500 hours for heat treatment.
3) Light resistance test: The test piece is treated with a fade meter tester at a temperature of 83 ° C. for 500 hours.

[Fiber fabric base material]
As the fiber fabric substrate, for example, woven fabric such as plain weave, knitted fabric such as circular knitting, non-woven fabric such as spunbond, etc. can be used.
Above all, preferred is a woven fabric or a knitted fabric from the viewpoint of easiness of sticking of synthetic leather.
The material of the woven or knitted fabric is not particularly limited, and examples thereof include polyester, nylon, rayon and the like, and polyester is preferable in terms of physical properties and price of the fabric.

[Resin layer]
The resin layer is a layer having at least a skin layer.
In addition, the resin layer may be laminated in the order of the skin layer and the intermediate layer.
An adhesive layer may be interposed between the fiber fabric base and the resin layer.

[Skin layer]
The skin layer is preferably a resin selected from the group consisting of a polyurethane resin, a polyvinyl chloride resin or a polyolefin resin. Among these, polyurethane resins and polyvinyl chloride resins are more preferable in terms of physical properties.

[Intermediate]
The intermediate layer is preferably a resin selected from the group consisting of polyurethane resin, polyvinyl chloride resin or polyolefin resin. Among these, polyurethane resins and polyvinyl chloride resins are more preferable in terms of physical properties. Also, the intermediate layer may be either a foam layer or a non-foam layer.
When the intermediate layer is a foamed layer, for example, a layer foamed by reaction of a polyurethane resin and water may be used, a layer foamed chemically by adding a foaming agent may be used, or a microballoon in which hollow particles are expanded is used The layer may be foamed. Thus, for example, a foaming agent or hollow fine particles may be added within a range that does not inhibit the adhesion to the fiber fabric substrate.

[Adhesive layer]
The adhesive layer is preferably a resin selected from the group consisting of a polyurethane resin, a polyvinyl chloride resin or a polyolefin resin. The adhesive layer may be either a foam layer or a non-foam layer.

  In addition, the resin constituting the skin layer, the intermediate layer and the adhesive layer may contain known additives such as a pigment, a filler, a dispersant, an antifoaming agent, a matting agent and a lubricant as long as the physical properties are not impaired. Good.

[Surface treatment layer]
The surface treatment layer of the present invention has a value measured by the wetting reagent of 60 dyne / cm or more, and after the 1) abrasion resistance test, 2) heat resistance test, and 3) light resistance test described later, respectively. It is not particularly limited as long as the measurement value by the wetting reagent of the surface treatment layer is 50 dyne / cm or more.

  The “measurement with a wetting reagent (wettability test)” in the surface treatment layer of the present invention is performed in accordance with JIS K6768. And, after performing each of 1) abrasion resistance test, 2) heat resistance test, and 3) light resistance test to be described later, “measurement by wetting reagent (wettability test)” in the surface treatment layer also conforms to JIS K6768. To be done.

1) Abrasion resistance test according to the present invention: In a plane abrasion machine, No. 9 canvas is set to the friction element, and a load is applied so that the load pressure applied to the test piece is 2 Mpa, and reciprocated 20,000 times.
In the 2) heat resistance test in the present invention, a test piece is placed in a gear oven, and is left at a temperature of 100 ° C. for 500 hours to perform heat treatment.
In the 3) light resistance test in the present invention, the test piece is treated with a fade meter tester at a temperature of 83 ° C. for 500 hours.
In addition, a test piece said here points out synthetic leather.

  The surface treatment layer preferably contains, for example, a water-dispersible polyurethane resin, a hydrophilic compound, and a crosslinking agent.

[Water-dispersed polyurethane resin]
As a water dispersion-type polyurethane resin, a polycarbonate-type polyurethane resin is preferable, for example from a durable viewpoint.

[Hydrophilic compound]
The hydrophilic compound is, for example, at least one hydrophilic compound selected from the group consisting of silicone hydrophilic compounds, polyurethane hydrophilic compounds, acrylic hydrophilic compounds, fluorine hydrophilic compounds, and water-soluble polymers. It can be mentioned.
Moreover, it is preferable to add the addition amount of a hydrophilic compound so that the sum total of solid content may be 10 to 200 parts with respect to 100 parts of solid content of water dispersion-type polyurethane resin.

[Crosslinking agent]
Examples of the crosslinking agent include one or more crosslinking agents selected from the group consisting of isocyanate type, carbodiimide type, and oxazoline type.
Moreover, as a crosslinking agent, the thing of non-yellowing type is more preferable.
When using an isocyanate type as a crosslinking agent, it is preferable to use block type isocyanate in order to reduce the reaction with water at normal temperature.
The addition amount of the crosslinking agent is preferably such that the total of the solid content is 0.5 to 50 parts with respect to 100 parts of the solid content of the water-dispersible polyurethane resin.

  Further, known additives such as pigments, antioxidants, ultraviolet absorbers, catalysts, inorganic fine particles such as silica, organic fillers and the like may be added to the surface treatment layer.

The surface treatment layer can be formed, for example, by preparing a coating agent containing a water-dispersed polyurethane resin, a hydrophilic compound, and a crosslinking agent, and coating the coating agent on the resin layer. The method for applying the coating agent is not particularly limited, but can be formed by a known method such as a gravure method or a reverse method.
Moreover, after apply | coating on a resin layer, the method of drying and forming, for example in a heating oven is preferable.
The temperature condition in drying is preferably 80 to 150 ° C., more preferably 120 to 140 ° C., from the viewpoint of the reactivity of the crosslinking agent.
The coating agent may contain a solvent such as an organic solvent or may be a non-solvent.

[Primer layer]
A primer layer may be provided between the surface treatment layer and the resin layer in order to improve the adhesion. The primer layer is a layer made of a resin, and may be added with known additives such as pigments, antioxidants, ultraviolet absorbers, catalysts, inorganic fine particles such as silica, organic fillers, and the like, as necessary.

  Hereinafter, the present invention will be described in detail based on examples.

(Preparation 1: Preparation of resin for skin layer in resin layer)
Main agent: 100 parts by weight of polycarbonate polyurethane resin ("Kisbon NY335FT" manufactured by DIC Corporation): 30 parts by weight of solvent: 10 parts by weight of ethyl acetate and 10 parts by weight of ethyl acetate: 10 parts by weight Preparation method: viscosity 800 mPa It was prepared to be sec (measured with a B-type viscometer by adjusting the liquid temperature to 25 ° C.).

(Formulation 2: Preparation of resin for adhesive layer)
Main agent: polycarbonate-based polyurethane resin (manufactured by DIC Corporation "Kisebo TA205FT"): 100 parts by weight Crosslinking agent: isocyanate-based crosslinking agent (manufactured by DIC Corporation "Burnock DN950"): 12 parts by weight Solvent: DMF 30 Parts by weight, and 30 parts by weight of MEK. Catalyst: 1 part by weight of "Kisbon Axel T81-E" manufactured by DIC Corporation Preparation method: Viscosity 800 mPa · sec (liquid temperature adjusted to 25 ° C and B-type viscometer Prepared.

(Formulation 3: Preparation of resin for surface treatment layer)
Main agent: Water-based polyurethane resin ("Lack coat WN 568 M" manufactured by Seiko Chemical Co., Ltd.): 100 parts by weight Cross-linking agent: Carbodiimide cross-linking agent ("Rack coat CL 7070" manufactured by Seiko Chemical Co., Ltd.): 10 parts by weight Hydrophilic Compound a: Fluorine-based compound (“Pararesin NC-700” manufactured by Ohara Palladium Chemical Co., Ltd.): 100 parts by weight • Hydrophilic Compound b: Polyurethane-based compound (“POLON MF13” manufactured by Shin-Etsu Chemical Co., Ltd.): 20 Preparation method by weight: The viscosity was adjusted to 800 mPa · sec (measured with a B-type viscometer by adjusting the liquid temperature to 25 ° C.).

(Preparation 4: Preparation of resin for surface treatment layer)
Main agent: Water-based polyurethane resin ("Lack coat WN 568M" manufactured by Seiko Chemical Co., Ltd.): 100 parts by weight Cross-linking agent: Carbodiimide cross-linking agent ("Rack coat CL 7070" manufactured by Seiko Chemical Co., Ltd.): 10 parts by weight : The viscosity was adjusted to 800 mPa · sec (measured with a B-type viscometer by adjusting the liquid temperature to 25 ° C.).

(Preparation 5: Preparation of resin for surface treatment layer)
Main agent: Water-based polyurethane resin ("Lack coat WN 568 M" manufactured by Seiko Chemical Co., Ltd.): 100 parts by weight Cross-linking agent: Carbodiimide cross-linking agent ("Rack coat CL 7070" manufactured by Seiko Chemical Co., Ltd.): 10 parts by weight Hydrophilic Compound b: polyurethane based compound (Shin-Etsu Chemical Co., Ltd. "POLON MF13"): 20 parts by weight · hydrophilic compound c: polyurethane based compound (Tanatex Chemicals Co., Ltd. "BAYPRET USV"): 100 parts by weight Preparation method: The viscosity was adjusted to 800 mPa · sec (measured with a B-type viscometer by adjusting the liquid temperature to 25 ° C.).

Example 1
The resin for the skin layer in the resin layer prepared according to the above-mentioned formulation 1 is coated on a release paper with a comma coater, the temperature is gradually raised from 80 ° C to 120 ° C, and after reaching 120 ° C, dried for 5 minutes, thickness A skin layer of about 15 μm resin layer was obtained.
Subsequently, the resin for an adhesive layer prepared according to the above-mentioned formulation 2 was applied on a skin layer formed on a release paper by a comma coater and dried at 120 ° C. to obtain an adhesive layer having a thickness of about 30 μm.
Subsequently, at the timing at which the adhesive layer exhibited adhesiveness, lamination of a fiber fabric substrate (a polyester fabric knitted from 150 denier polyester yarn with a circular knitting machine) was performed.
Subsequently, after taking up in a roll, this is matured at 50 ° C. for 48 hours, and then the release paper is peeled off, and the fiber fabric substrate, the adhesive layer, and the skin layer are laminated in this order. I got leather.

  Subsequently, the resin for surface treatment layer prepared according to the above-mentioned formulation 3 is coated on the obtained synthetic leather with a gravure roll, heated at 130 ° C. in a continuous oven, and then heated to 50 ° C. Aging was performed for 48 hours to obtain a synthetic leather provided with a surface treatment layer having a coating thickness of about 2 μm.

(Measurement with wetting reagent (wettability test) and dirt test before each test)
The synthetic leather provided with the obtained surface treatment layer was used as a test piece, and the wettability test and the soiling test on the surface treatment layer of this test piece were performed. The results are shown in Table 1.

(Measurement after each test (wettability test) and stain test)
The test pieces were subjected to 1) abrasion resistance test, 2) heat resistance test and 3) light resistance test respectively, and then the wettability test and the soiling test on the surface treatment layer of the test piece after each test. Did. The results are shown in Table 1.

(Measurement by wetting reagent (wettability test))
The measurement with the wetting reagent (wettability test) was performed according to JIS K6768.

(Staining test)
With respect to the test piece, the color difference ΔE was measured before and after “scrubbing”.
The term "scrubing" used herein refers to first rubbing a soiled cloth (EMPA # 104) on a test piece at a load pressure of 2 MPa with a flat-type abrasion tester 1000 times, and then replacing the soiled cloth with a new one. Repeat the same operation a total of 3 times and rub the test piece a total of 3000 times.
Subsequently, a white cloth sufficiently moistened with distilled water is rubbed ten times with a flat-type abrasion tester under a load pressure of 30 kPa against a test piece which has been soiled with a soiled cloth.

(Abrasion resistance test)
The abrasion resistance test is a method of setting No. 9 canvas to the friction element in a flat type wear tester, applying load so that the load pressure applied to the test piece is 2 Mpa, and reciprocate 20,000 times.

(Heat resistance test)
In the heat resistance test, a test piece is placed in a gear oven and allowed to stand at a temperature of 100 ° C. for 500 hours for heat treatment.

(Light resistance test)
The light resistance test is a method of treating the test piece with a fade meter tester at a temperature of 83 ° C. for 500 hours.

(Comparative example 1)
A synthetic leather provided with a surface treatment agent was obtained in the same manner as in Example 1 except that the resin for surface treatment layer prepared according to the above-mentioned Formulation 4 was used as the surface treatment layer.
The obtained synthetic leather was subjected to measurement using a wetting reagent (wettability test) and a stain test. The results are shown in Table 1.
Further, in the same manner as in Example 1, the results of measurement (wettability test) by the wetting reagent after each test and the stain test are shown in the evaluation 1.

  The results of the stain test were ΔE> 5 in all after the abrasion resistance test, after the heat resistance test, and after the light resistance test, and the result was inferior to Example 1.

(Comparative example 2)
A synthetic leather provided with a surface treatment agent was obtained in the same manner as in Example 1 except that the resin for surface treatment layer prepared according to the above-mentioned Formulation 5 was used as the surface treatment layer.
The obtained synthetic leather was subjected to measurement using a wetting reagent (wettability test) and a stain test. The results are shown in Table 1.
Further, in the same manner as in Example 1, the results of measurement (wettability test) by the wetting reagent after each test and the stain test are shown in the evaluation 1.

  The result of the stain test was ΔE> 5 after the heat resistance test and after the light resistance test, and the result was inferior to that of Example 1.

Claims (4)

In synthetic leather laminated in the order of at least a fiber fabric base, a resin layer, and a surface treatment layer,
The surface treatment layer of the synthetic leather has a value measured by the wetting reagent of 60 dyne / cm or more, and after 1) the abrasion resistance test, 2) the heat resistance test, and 3) the light resistance test shown below. A synthetic leather having antifouling performance characterized in that the measured value of the surface treatment layer by a wetting reagent is 50 dyne / cm or more.
1) Wear resistance test: In a flat wear machine, set # 9 canvas on the friction element, apply a load so that the load pressure applied to the test piece is 2 Mpa, and reciprocate 20,000 times.
2) Heat resistance test: The test piece is placed in a gear oven and left to stand at a temperature of 100 ° C. for 500 hours for heat treatment.
3) Light resistance test: The test piece is treated with a fade meter tester at a temperature of 83 ° C. for 500 hours.   The surface treatment layer contains a water-dispersed polyurethane resin, a hydrophilic compound, and a crosslinking agent, and the hydrophilic compound is a silicone-based hydrophilic compound, a polyurethane-based hydrophilic compound, an acrylic-based hydrophilic compound, It is 1 or more types selected from the group which consists of a fluorine-type hydrophilic compound and a water-soluble polymer compound, The synthetic leather which has the antifouling performance of Claim 1 characterized by the above-mentioned.   The said crosslinker consists of 1 or more types selected from the group which consists of isocyanate type, a carbodiimide type, and an oxazoline type | system | group, The synthetic leather which has the antifouling performance of Claim 1 or 2 characterized by the above-mentioned.   The synthetic leather having antifouling performance according to any one of claims 1 to 3, wherein the resin layer is at least one selected from the group consisting of a polyurethane resin, a polyvinyl chloride resin, and a polyolefin resin. .