CN110520568B - Artificial leather substrate and grain-surface artificial leather - Google Patents

Artificial leather substrate and grain-surface artificial leather Download PDF

Info

Publication number
CN110520568B
CN110520568B CN201880024689.8A CN201880024689A CN110520568B CN 110520568 B CN110520568 B CN 110520568B CN 201880024689 A CN201880024689 A CN 201880024689A CN 110520568 B CN110520568 B CN 110520568B
Authority
CN
China
Prior art keywords
artificial leather
grain
leather substrate
hardness
polymer elastomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201880024689.8A
Other languages
Chinese (zh)
Other versions
CN110520568A (en
Inventor
中山公男
佐藤隼纪
成本直人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Publication of CN110520568A publication Critical patent/CN110520568A/en
Application granted granted Critical
Publication of CN110520568B publication Critical patent/CN110520568B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0013—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using multilayer webs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0068—Polymeric granules, particles or powder, e.g. core-shell particles, microcapsules
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/042—Acrylic polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/10—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
    • D06N3/106—Elastomers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0263—Polyamide fibres

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The present invention provides an artificial leather substrate comprising: a fabric, and a polymer elastomer, fine particles and a plasticizer which are provided to the fabric, wherein the polymer elastomer comprises a (meth) acrylic polymer elastomer and polyurethane, the fine particles have a Mohs hardness of 4 or less, and the product of the hardness and the Shore C hardness and the thickness is 200 to 400mm 2 . Further disclosed is a grain-finished artificial leather obtained by using such an artificial leather substrate.

Description

Artificial leather substrate and grain-surface artificial leather
Technical Field
The present invention relates to an artificial leather substrate and grain-finished artificial leather using the same.
Background
Conventionally, there has been known a grain-faced artificial leather in which a grain-faced resin layer is laminated on an artificial leather substrate obtained by impregnating voids provided in a fabric with a polymeric elastomer. As an alternative to natural leather, grain-finished artificial leather has been used as a skin material for shoes, clothes, gloves, leather bags, balls, etc., interior materials for buildings, vehicles, and the like.
The natural leather has flexibility and a sense of fullness due to the inclusion of the dense collagen fibers. The sense of fullness of natural leather means that fine wrinkles having a high quality feel are formed with arcs when bent. Further, the grain leather has excellent surface flatness, and even when the grain leather is formed into a flat grain, the unevenness is not conspicuous. However, it is difficult to obtain natural leather having stable quality. Further, collagen fibers have low heat resistance and water resistance. Therefore, it is difficult to use natural leather for applications requiring heat resistance and water resistance. In order to improve the heat resistance and water resistance of natural leather, there is a method of thickening a grain-side resin layer (hereinafter, also simply referred to as a grain-side layer). However, in the case of thickening the grain layer, the flexibility, which is an advantage of natural leather, is reduced.
On the other hand, grain-finished artificial leather is excellent in quality stability, heat resistance, water resistance, abrasion resistance, and maintenance properties. But has the following problems. The grain-finished artificial leather has a reduced feeling of fullness because voids of the polymeric elastomer are not filled in the interior of the fabric. Therefore, when grain-finished artificial leather is curved, the artificial leather is not bent in a circular arc like grain-finished leather, and is buckled and bent to form rough wrinkles.
As grain-faced artificial leather for solving the above problems, for example, patent document 1 below discloses grain-faced artificial leather having a high sense of fullness, which is obtained by laminating a grain resin layer on an artificial leather substrate containing a filler, a liquid nonvolatile oil and a polymeric elastomer.
Documents of the prior art
Patent document
Patent document 1: WO2014/132630 pamphlet
Disclosure of Invention
Problems to be solved by the invention
As described above, the grain-finished artificial leather contains voids in the fabric. Therefore, grain-finished artificial leather has a lower fullness than grain-finished leather, and when grain-finished artificial leather is flexed, the following disadvantages occur: unlike grain leather, which is natural leather, the leather is bent in a circular arc shape and buckled to form rough wrinkles. In particular, in the case of grain-finished artificial leather having a thin grain layer or a plain grain layer such as a mirror surface, wrinkles tend to become uneven, and coarse wrinkles may occur to reduce the high-grade feeling of grain-finished artificial leather. In order to reduce such a lack of fullness, unevenness of wrinkles, and occurrence of rough wrinkles, when the content of the polymer elastomer to be added to the fabric is increased, the grain-finished artificial leather has a stiff texture like rubber due to the resilient feeling of the polymer elastomer. In addition, as another problem, there is a disadvantage that the surface flatness is poor.
The purpose of the present invention is to provide a grain-finished artificial leather having both flexibility and a feeling of fullness, having fine wrinkles caused by bending in a circular arc shape during bending, and having excellent surface flatness.
Means for solving the problems
One aspect of the present invention is an artificial leather substrate comprising: fabric and method for imparting sameA polymeric elastomer of a silk, fine particles and a plasticizer, wherein the polymeric elastomer comprises a (meth) acrylic polymeric elastomer and polyurethane, the fine particles have a Mohs hardness of 4 or less, and the product of a hardness of hardness, a Shore C hardness and a thickness of 200 to 400mm 2 . By using such an artificial leather substrate, it is possible to produce grain-finished artificial leather having both flexibility and a feeling of fullness as in grain-finished leather, having fine wrinkles due to rounding at the time of bending, and having excellent surface flatness.
Another aspect of the present invention is grain-faced artificial leather comprising the artificial leather substrate described above and a grain-faced resin layer formed on at least one side of the artificial leather substrate. The grain-surface artificial leather has flexibility and a sense of fullness, is provided with a circular arc when being bent, and is easy to form fine wrinkles.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to obtain grain-finished artificial leather having both flexibility and a feeling of fullness, having fine wrinkles due to rounding at the time of bending, and having excellent surface flatness.
Detailed Description
The artificial leather substrate of the present embodiment comprises a fabric, and a polymeric elastomer, fine particles and a plasticizer which are provided to the fabric, wherein the polymeric elastomer comprises a (meth) acrylic polymeric elastomer and polyurethane, the fine particles have a mohs hardness of 4 or less, and the product of the hardness, the shore C hardness and the thickness is 200 to 400mm 2 . Hereinafter, the artificial leather substrate of the present embodiment will be described in detail.
Examples of the fabric include a fiber structure including a nonwoven fabric, a woven fabric, and a knitted fabric. Among them, nonwoven fabrics are particularly preferable because of their low unevenness in density of the fibers, and hence, they can easily give an artificial leather substrate having flexibility, a solid feeling, and surface flatness. Hereinafter, a case of using a nonwoven fabric will be described in detail as a representative example.
The average fineness of the fibers is preferably 0.001 to 2.5dtex, more preferably 0.001 to 0.9dtex, particularly preferably 0.001 to 0.7dtex, more preferably 0.001 to 0.5dtex, and more preferably 0.001 to 0.3 dtex. The fineness of the fibers can be measured by imaging a cross section of the artificial leather substrate in the thickness direction at a magnification of 2000 times with a Scanning Electron Microscope (SEM). Specifically, the fiber fineness can be calculated by measuring the cross-sectional area of the fiber from the photograph obtained by SEM and based on the cross-sectional area and the specific gravity of the resin forming the fiber. The average fineness can be determined as an average value of the average fineness of 100 fibers which is sufficiently determined from the photograph.
The fiber-forming resin is not particularly limited, and examples thereof include: polyamides (nylons) such as polyamide 6, polyamide 66, polyamide 10, polyamide 11, polyamide 12, and polyamide 6-12; aromatic polyesters such as polyethylene terephthalate (PET), isophthalic acid-modified PET, sulfoisophthalic acid-modified PET, polybutylene terephthalate, and polyhexamethylene terephthalate; aliphatic polyesters such as polylactic acid, polyethylene glycol succinate, polybutylene succinate adipate, polyhydroxybutyrate-polyhydroxyvalerate resins, and the like; polyolefins such as polypropylene, polyethylene, polybutene, polymethylpentene, and chlorinated polyolefins. These compounds may be used alone, or two or more of them may be used in combination. Among them, PET or modified PET is preferable; polylactic acid; polyamide 6, polyamide 12, polyamide 6-12; polypropylene. Polyamide is particularly preferable from the viewpoint of forming an artificial leather substrate having more flexibility and more excellent surface flatness. In addition, additives such as softening agents, carding agents, antifouling agents, hydrophilizing agents, lubricants, deterioration-preventing agents, ultraviolet absorbers, flame retardants, and the like may be added to the fibers as necessary within a range not to impair the effects of the present invention.
The content ratio of the fabric in the artificial leather substrate is not particularly limited, and is preferably 25 to 69.5 mass% from the viewpoint that an artificial leather substrate having excellent balance among form stability, flexibility, and flatness can be obtained.
The polymer elastomer includes at least a (meth) acrylic polymer elastomer and polyurethane. The polymer elastomer restrains fibers forming the fabric and imparts form stability, flexibility, fullness and the like to the artificial leather base material. The (meth) acrylic polymer elastomer can impart flexibility, surface flatness, fine wrinkles, and a feeling of fullness to the surface. In addition, polyurethane can impart form stability, mechanical properties, and rigidity, in particular.
The (meth) acrylic polymer elastomer can be obtained by combining ethylenically unsaturated monomers, and specifically, can be obtained by appropriately combining and polymerizing various monomers of ethylenically unsaturated monomers, a crosslinkable monomer used as needed, and the like. The expression "(meth) acrylic" means acrylic or methacrylic.
Specific examples of the ethylenically unsaturated monomer include: 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl (meth) acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, diacetone acrylamide, isobutyl methacrylate, isopropyl methacrylate, acrylic acid, methacrylic acid, acrylamide, acrylonitrile, styrene, alpha-methylstyrene, p-methylstyrene, (meth) acrylamide, diacetone (meth) acrylamide, methyl methacrylate, maleic acid, itaconic acid, fumaric acid, cyclohexyl methacrylate, dimethylaminoethyl methacrylate, lauryl methacrylate, n-butyl acrylate, isobutyl acrylate, isopropyl methacrylate, acrylic acid, methacrylic acid, acrylamide, acrylonitrile, styrene, alpha-methylstyrene, p-methyl (meth) acrylamide, diacetone (meth) acrylamide, methyl methacrylate, maleic acid, itaconic acid, fumaric acid, cyclohexyl methacrylate, dimethylaminoethyl methacrylate, methyl methacrylate, and mixtures thereof, Diethylaminoethyl methacrylate, vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, vinyl amide, ethylene, propylene, vinyl pyrrolidone, isopropyl acrylate, n-hexyl methacrylate, n-hexyl acrylate, methyl acrylate, n-butyl methacrylate, hydroxypropyl methacrylate, vinyl acetate, methyl acrylate, n-butyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like. These compounds may be used alone, or two or more of them may be used in combination.
The crosslinkable monomer is a monomer for forming a crosslinked structure with the (meth) acrylic polymer elastomer. Specific examples of the crosslinkable monomer include: polyfunctional ethylenically unsaturated monomers such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate; various monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; polyfunctional ethylenically unsaturated monomers having a reactive group capable of forming a crosslinked structure, such as (meth) acrylic acid derivatives having an epoxy group, such as glycidyl (meth) acrylate.
In particular, the glass transition temperature (Tg) of the (meth) acrylic polymer elastomer is preferably-60 to 10 ℃ and more preferably-50 to-5 ℃ from the viewpoint of easily obtaining a flexible artificial leather substrate. When the Tg of the (meth) acrylic polymer elastomer is too low, the adhesiveness is increased, and problems may occur in the production process and in practical use.
The 100% modulus of the (meth) acrylic polymer elastomer is preferably 0.4 to 5MPa, and more preferably 0.7 to 4 MPa. In the case where the amount is within this range, the (meth) acrylic polymer elastomer sufficiently restrains the fibers of the fabric, and thus a particularly flexible artificial leather substrate can be easily obtained.
As the polyurethane, there can be used, without particular limitation, a polyurethane conventionally used in the production of artificial leather substrates. Specific examples thereof include: various polyurethanes such as polycarbonate polyurethane and polyether polyurethane obtained by reacting a polymer polyol having an average molecular weight of 200 to 6000, an organic polyisocyanate and a chain extender at a predetermined molar ratio. Particularly, from the viewpoint of excellent durability, a polyurethane containing a polycarbonate polyurethane in an amount of 60 mass% or more is preferable.
The 100% modulus of the polyurethane is preferably 1 to 10MPa, and more preferably 2 to 8 MPa. In the case of such a range, a flexible artificial leather substrate excellent in form stability and mechanical properties can be easily obtained.
The content of the polymeric elastomer in the artificial leather substrate is preferably 15 to 40 mass%. In the case of such a range, an artificial leather substrate which is excellent in a sense of fullness and surface flatness and which is easily bent in a circular arc at the time of bending and is likely to generate fine wrinkles can be easily obtained.
The content of the (meth) acrylic polymer elastomer is preferably 5 to 90% by mass, and more preferably 5 to 70% by mass, based on the total amount of the polyurethane and the (meth) acrylic polymer elastomer.
The artificial leather substrate comprises fine particles having a Mohs hardness of 4 or less, preferably 0.5 to 4. Examples of the fine particles having a mohs hardness of 4 or less include: metals having a mohs hardness of 4 or less, metal oxides, inorganic compounds, organic compounds, inorganic-organic compounds, and the like. Fine particles having a mohs hardness of 4 or less impart an excellent feeling of fullness and surface flatness to an artificial leather substrate, and are bent with a circular arc when bent, so that fine wrinkles are likely to occur.
Typical particle hardnesses are for example: graphite (Mohs hardness 0.5-1, the same below), talc (1), gypsum (1), lead (1.5), calcium sulfate (1.6-2), zinc (2), silver (2), amber (2-2.5), aluminum silicate (2-2.5), cerium oxide (2.5), magnesium hydroxide (2-3), mica (2.8), aluminum (2-2.9), aluminum hydroxide (3), calcium carbonate (3), magnesium carbonate (3-4), marble (3-4), copper (2.5-4), brass (3-4), magnesium oxide (4), zinc oxide (4-5), iron (4-5), glass (5), iron oxide (6), titanium oxide (5.5-7.5), silicon dioxide (7), aluminum oxide (9), silicon carbide (9) and diamond (10). The artificial leather substrate of the present embodiment contains fine particles having a mohs hardness of 4 or less. In the case where the mohs hardness of the microparticles exceeds 4, the compliance is reduced. The mohs hardness can be measured by a known method. In addition to the mohs hardness, the hardness is known as new mohs hardness, vickers Hardness (HV), shore Hardness (HS), knoop hardness, and the like. The Mohs hardness of 1 to 4 corresponds to 1 to 350 of Vickers Hardness (HV), 1 to 40 of Shore Hardness (HS), and 1 to 300 of Knoop hardness. In the present embodiment, fine particles having a hardness measured by another hardness measuring method corresponding to fine particles having a mohs hardness of 4 or less are also included.
Examples of the fine particles having a mohs hardness of 4 or less (hereinafter, also simply referred to as "fine particles") include: graphite, talc, gypsum, calcium sulfate, amber, aluminum silicate, magnesium hydroxide, mica, aluminum hydroxide, calcium carbonate, magnesium oxide. Among them, talc, magnesium silicate, calcium sulfate, aluminum silicate, calcium carbonate, magnesium oxide, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, and mica are particularly preferable because they are excellent in chemical stability and thermal stability and can easily obtain fine particles having a uniform particle diameter and high purity. These fine particles may be used alone, or two or more kinds may be used in combination.
The chemical stability is a property of being hardly swollen or dissolved in water or hot water in a pH range in practical use, for example, pH4 to 12. The thermal stability is a characteristic of having a thermal decomposition temperature and a melting point of 150 ℃ or higher, preferably 200 ℃ or higher. The solubility of the fine particles is preferably 1% or less. In addition, fine particles having a mohs hardness of more than 4 may be included in the range not impairing the effects of the present invention, in addition to fine particles having a mohs hardness of 4 or less. In addition, for example, a softener, a carding agent, an antifouling agent, a hydrophilizing agent, a lubricant, an anti-deterioration agent, an ultraviolet absorber, a flame retardant, and the like may be used in combination.
The average particle diameter of the fine particles is preferably 0.5 to 10 μm, and more preferably 1 to 7 μm, from the viewpoint of easily providing uniform voids in the fabric. When the average particle size is too small, the artificial leather substrate tends to become hard.
Further, the particles preferably have a true specific gravity of 1.2 to 4.5g/cm from the viewpoint of easily providing uniform voids in the fabric and easily obtaining an artificial leather substrate particularly excellent in a feeling of fullness 3 。
The content of the fine particles is preferably 15 to 40% by mass of the artificial leather substrate, because the artificial leather substrate is easily provided with a solid feeling and excellent surface flatness, and is easily folded in a circular arc shape during bending to easily form fine wrinkles. When the content ratio of the fine particles is too high, the surface flatness tends to be easily lowered.
Further, the ratio of the (meth) acrylic elastomer to the total amount of the fine particles and the (meth) acrylic elastomer is such that the hardness and shore C hardness can be easily obtainedThe product of the thickness and the thickness is 200-400 mm 2 The amount of the (b) is preferably 5 to 50% by mass, and more preferably 5 to 40% by mass.
The artificial leather substrate of the present embodiment contains a plasticizer. The plasticizer is blended to soften the fabric, the polymer elastomer, and the fine particles to improve the plastic deformability. Examples of the plasticizer include: liquid, viscous, waxy, solid fats and oils or fatty acid esters. Specific examples thereof include: hydrocarbon oils such as fatty acid esters and paraffin oils, hydrocarbon waxes, carnauba wax, phthalic acid esters, phosphoric acid esters, and hydroxycarboxylic acid esters. These plasticizers may be used alone, or two or more of them may be used in combination. Among them, from the viewpoint of obtaining an artificial leather substrate having both flexibility and a feeling of fullness, a plasticizer having a melting point of 60 ℃ or less, preferably a liquid state at 23 ℃, particularly a fatty acid ester is preferable.
The fatty acid ester is a compound obtained by esterifying an alcohol with an acid. Specific examples thereof include: monohydric alcohol esters, monohydric alcohol esters of polybasic acids, fatty acid esters of polyhydric alcohols and derivatives thereof, fatty acid esters of glycerol, and the like. Examples of the alcohol include: methanol, isopropanol, n-butanol, isobutanol, n-octanol, 2-ethylhexanol, n-decanol, isodecanol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, octyldodecanol, glycerin, sorbitan, polyoxyethylene sorbitol, ethylene glycol, polyethylene glycol, propylene glycol, pentaerythritol, polyoxyethylene bisphenol a, and the like. In addition, examples of the acid include: octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, coconut oil acid, methacrylic acid, 2-ethylhexanoic acid, phthalic acid, adipic acid, azelaic acid, maleic acid, sebacic acid, trimellitic acid, and the like.
Specific examples of the fatty acid ester include: cetyl 2-ethylhexanoate, methyl cocoate, methyl laurate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, octyldodecyl myristate, methyl stearate, butyl stearate, 2-ethylhexyl stearate, isotridecyl stearate, methyl oleate, myristyl myristate, stearyl stearate, isobutyl oleate, di-n-alkyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, didecyl phthalate, ditridecyl phthalate, tri-n-alkyl trimellitate, tri-2-ethylhexyl trimellitate, triisodecyl trimellitate, diisobutyl adipate, diisodecyl adipate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sodium lauryl sulfate, sodium lauryl sulfate, Sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monostearate, sorbitan sesquioleate, sorbitan monolaurate, sorbitan monopalmitate, polyoxyethylene sorbitan monolaurate, polyoxyethylene monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene trioleate, polyoxyethylene sorbitan tetraoleate, sorbitan monolaurate, polyoxyethylene monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, polyethylene glycol bisphenol A laurate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, glycerol monostearate, glycerol sesquioleate, sorbitol monolaurate, polyoxyethylene monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monostearate, or the like, Stearic acid monoglyceride, palmitic acid monoglyceride, oleic acid monoglyceride, stearic acid mono/diglyceride, 2-ethylhexanoic acid triglyceride, behenic acid monoglyceride, caprylic acid mono/diglyceride, caprylic acid triglyceride, lauryl methacrylate, and the like.
Among the fatty acid esters, in particular, from the viewpoint of easily obtaining an artificial leather substrate having both flexibility and a feeling of fullness, a fatty acid ester having a melting point of 60 ℃ or less, preferably a liquid state at 23 ℃, is preferable, and a fatty acid ester of a fatty acid having 12 to 18 carbon atoms and a polyhydric alcohol is particularly preferable.
The content of the plasticizer is not particularly limited, and is preferably 0.5 to 5% by mass, more preferably 1 to 5% by mass, and particularly preferably 2 to 4% by mass in the artificial leather substrate, from the viewpoint of sufficiently exhibiting the effect of improving the flexibility. If the content of the plasticizer is too high, the flame retardancy tends to be lowered, and the resulting film tends to bleed out and become sticky.
In the artificial leather substrate of the embodiment, the product of the hardness, the Shore C hardness and the thickness is 200-400 mm 2 . For existing artificial leather substrates, the relationship of surface hardness to flexibility is a trade-off relationship. The artificial leather base material of the embodiment adjusts the product of hardness, Shore C hardness and thickness to 200-400 mm 2 Thereby having both high surface hardness and flexibility. The product of hardness, Shore C hardness and thickness is 200-400 mm 2 Preferably 210 to 350 mm. The product of hardness of softness, Shore C hardness and thickness is less than 200mm 2 In the case of (2), either the surface hardness or the compliance is insufficient, and coarse wrinkles are likely to occur. In addition, the product of hardness, Shore C hardness and thickness exceeds 400mm 2 In the case of (2), an artificial leather substrate which is soft and lacks a solid feeling, or whose surface is too hard and is liable to cause dead folds, can be easily obtained.
The softness represents the degree of flexibility of the artificial leather substrate. The hardness of the artificial leather substrate is measured by a softness tester. The hardness of the artificial leather substrate is preferably 1.8 to 6mm, and more preferably 2 to 5mm, from the viewpoint of obtaining an artificial leather substrate having an excellent balance between flexibility and a feeling of fullness. In the case of producing a grain-finished artificial leather, the hardness is preferably measured from the surface on which the grain layer is formed.
The shore C hardness represents a surface hardness. The Shore C hardness of the artificial leather substrate is preferably 48 to 80, more preferably 52 to 76, in view of obtaining an artificial leather substrate having particularly high surface flatness and particularly easily exhibiting fine wrinkles. The shore C hardness is measured on the same side as the side on which the hardness is measured, and in the case of artificial leather having a grain top layer, it is preferable to measure the side on which the grain top layer is formed.
The thickness of the artificial leather substrate is not particularly limited, and the product of hardness, Shore C hardness and thickness is 200-400 mm 2 Artificial leatherIn view of the base material, the thickness is preferably 100 to 3000 μm, and more preferably about 300 to 2000 μm.
The product of hardness, Shore C hardness and thickness is easily obtained and is 200-400 mm 2 In view of the artificial leather substrate, the apparent density of the artificial leather substrate is preferably 0.45 to 0.85g/cm 3 More preferably 0.55 to 0.80g/cm 3 . In particular, when a nonwoven fabric using an ultrafine fiber of a polyamide-based fiber is used as a fabric, the apparent density is preferably 0.55 to 0.80g/cm 3 More preferably 0.60 to 0.75g/cm 3 。
In addition, the total of the apparent density of the fine particles having a Mohs hardness of 4 or less and the apparent density of the (meth) acrylic polymer elastomer in the artificial leather substrate is such that the product of the hardness of the artificial leather, the Shore C hardness and the thickness is 200 to 400mm 2 The base material of the artificial leather is preferably 0.15 to 0.40g/cm 3 。
Next, a method for producing the artificial leather substrate will be described. In the present embodiment, a case where a nonwoven fabric made of ultrafine fibers is used as a fabric will be described in detail as a typical example.
The nonwoven fabric of ultrafine fibers can be obtained by, for example, entangling ultrafine fiber-generating fibers such as sea-island (matrix-domain) composite fibers and then performing ultrafine fiber treatment. In the present embodiment, the case of using the sea-island type composite fiber will be described in detail, but an ultrafine fiber generating fiber other than the sea-island type composite fiber may be used. Further, the ultrafine fibers can be directly spun without using the ultrafine fiber generating fibers. Specific examples of the ultrafine fiber-forming fiber other than the sea-island type composite fiber include: split fibers, petal-shaped fibers, and the like.
Examples of the method for producing the ultrafine fiber nonwoven fabric include the following methods: the sea-island type composite fiber is melt-spun using a thermoplastic resin of a sea component and a thermoplastic resin of an island component to produce a web, and after the web is subjected to a cohesion treatment, the sea component is selectively removed from the sea-island type composite fiber to form an ultrafine fiber composed of the thermoplastic resin of the island component.
As the thermoplastic resin of the sea component, a thermoplastic resin different from the thermoplastic resin of the island component in solubility in a solvent or degradability in a decomposer can be selected. Specific examples of the thermoplastic resin constituting the sea component include: water-soluble polyvinyl alcohol resins, polyethylene, polypropylene, polystyrene, ethylene-propylene resins, ethylene-vinyl acetate resins, styrene-ethylene resins, styrene-acrylic resins, and the like.
As a method for producing a web, the following methods can be mentioned: a method of collecting a sea-island type composite fiber of a long fiber spun by a spunbond method or the like on a web without cutting to form a long fiber web, a method of cutting a long fiber into a short fiber to form a short fiber web, or the like. Among them, a long fiber web is particularly preferable in terms of excellent denseness and a feeling of fullness. The long fibers do not mean short fibers formed by intentional cutting after spinning, but mean continuous fibers. More specifically, the term "fibers" means fibers which are not intentionally cut into short fibers having a fiber length of about 3 to 80 mm. The sea-island type composite fiber before the ultrafine fibers is preferably 100mm or more in fiber length, technically producible, and may have a fiber length of several meters, several hundreds of meters, several km or more as long as it is not inevitably cut in the production process. In the production process, a part of the long fibers may be inevitably cut to form short fibers due to needle punching and surface polishing at the time of holding. In addition, a melt-bonding treatment may be performed to impart form stability to the formed web.
The wrapping treatment may be, for example, a method of laminating about 5 to 100 sheets of net and performing needle punching or high-pressure water jet treatment.
In the production of a nonwoven fabric of ultrafine fibers, a thermoplastic resin constituting a sea component (matrix component) of a sea-island type composite fiber, which is selectively removable, and a thermoplastic resin constituting an island component (domain component) of the sea-island type composite fiber, which is a resin component forming ultrafine fibers, are first melt-spun and drawn to obtain the sea-island type composite fiber.
The sea-island type composite fiber can be densified by performing a fiber shrinking treatment such as wet heat shrinking treatment by water vapor in an arbitrary step before the sea component of the sea-island type composite fiber is removed to form an ultrafine fiber, and the feeling of fullness can be improved.
The sea component of the sea-island type composite fiber is dissolved or decomposed at an appropriate stage after the formation of the web and removed. By such removal by decomposition or removal by dissolution and extraction, the sea-island type composite fiber is made very fine, and a fiber bundle-like ultrafine fiber is formed.
The method for applying the (meth) acrylic polymer elastomer or the polymer elastomer including polyurethane to the fabric is not particularly limited. As an example, there is a method of impregnating a fabric with a dispersion obtained by mixing an emulsion or aqueous dispersion of a (meth) acrylic polymer elastomer and an emulsion or aqueous dispersion of polyurethane, and then drying the impregnated fabric. As another example, either the polyurethane-based polymer elastomer or the (meth) acrylic polymer elastomer may be applied to the fabric in advance, and then only the other may be applied. In the case of using a nonwoven fabric of ultrafine fibers made of a sea-island type composite fiber, these polymeric elastomers may be applied to a nonwoven fabric of a sea-island type composite fiber before the ultrafine fibers are formed, or may be applied to a nonwoven fabric of an ultrafine fiber.
When the ultrafine fibers are formed as fiber bundles derived from ultrafine fiber-generating fibers, the elastic polymer may be impregnated into the fiber bundles, may be attached to the outside of the fiber bundles, or may be attached to the inside and the outside of the fiber bundles. When the polymer elastic body is impregnated into the fiber bundle, the hand can be adjusted by adjusting the restraint of the ultrafine fibers forming the fiber bundle. For example, when the sea-island type composite fiber is subjected to the ultrafine fiber treatment, the water-soluble thermoplastic resin is removed from the sea-island type composite fiber to form voids in the ultrafine fiber bundle. The dispersion of the polymer elastomer is likely to enter the thus-formed voids by capillary action. Therefore, when the polymeric elastomer is provided inside the fiber bundle, the form stability of the nonwoven fabric is improved.
The method for providing the (meth) acrylic polymer elastomer, polyurethane, fine particles, and plasticizer to the voids of the fabric is not particularly limited. Specifically, for example, the following methods are mentioned: a fabric is impregnated with a dispersion liquid containing polyurethane, (meth) acrylic polymer elastomer, fine particles, and a plasticizer, and dried to give the fabric.
In the case where the fabric is a nonwoven fabric of ultrafine fibers made of a sea-island type composite fiber, it is preferable from the viewpoint of production steps that polyurethane is applied and ultrafine is performed before the sea-island type composite fiber is extremely refined, and then a dispersion containing a (meth) acrylic polymer elastomer, fine particles, and a plasticizer is applied and dried. In addition, according to such a step, it is also possible to add the (meth) acrylic polymer elastomer, the fine particles, and the plasticizer to the inside of the fiber bundle of the ultrafine fibers, which is preferable in view of the above. When the (meth) acrylic polymer elastomer and the plasticizer are added before the sea-island type composite fiber is extremely refined, the (meth) acrylic polymer elastomer is deteriorated and deformed by the treatment in the extremely refining step, and the plasticizer is easily dropped.
In addition, when the fabric is a nonwoven fabric of ultrafine fibers made of a sea-island type composite fiber, the following can be provided: the sea-island type composite fiber is provided with polyurethane and fine particles before being extremely refined, and is provided with a dispersion liquid containing a (meth) acrylic polymer elastomer and a plasticizer after being extremely refined, and is dried.
In the case where the fabric is a nonwoven fabric of ultrafine fibers made of a sea-island type composite fiber, the fine particles, polyurethane, and (meth) acrylic polymer elastomer may be added before the sea-island type composite fiber is extremely refined, and after the sea-island type composite fiber is extremely refined, an aqueous dispersion containing a plasticizer may be added and dried. According to such a step, the fine particles and the polymer elastomer can be easily mixed and uniformly applied.
In view of the ease with which the effects of the present invention are particularly exhibited to a great extent, it is preferable that the fine particles be present inside the polymer elastomer.
Thereby, the artificial leather substrate of the present embodiment can be obtained. The artificial leather substrate may be subjected to a thickness adjustment and flattening treatment by a dicing treatment or a polishing treatment, or a finishing treatment such as a kneading softening treatment (softening by softening), a vacuum softening treatment (softening by softening), a reverse sealing brushing treatment, an antifouling treatment, a hydrophilization treatment, a lubricant treatment, a softener treatment, an antioxidant treatment, an ultraviolet absorber treatment, a fluorescer treatment, or a flame retardant treatment, as required.
In addition, it is preferable to perform a softening process on the artificial leather substrate for the purpose of adjusting the fullness and flexibility of the artificial leather substrate. The method of the softening treatment is not particularly limited. Specifically, for example, a method is preferred in which an artificial leather substrate is brought into close contact with an elastomer sheet, mechanically contracted in the machine direction (MD of the production line), and heat-treated in the contracted state to be heat-set. By such a method, the flatness of the artificial leather substrate can be improved and the artificial leather substrate can be softened.
The artificial leather substrate may be subjected to a thickness adjustment and a flattening treatment by a dicing treatment and a polishing treatment, if necessary.
The artificial leather substrate of the present embodiment can be preferably used for the production of grain-finished artificial leather having a grain layer formed on an artificial leather substrate. The grain layer may be a single-layer resin layer or a multilayer structure including a plurality of layers such as a resin layer including a skin layer and an adhesive layer.
The method for forming the grain layer on the artificial leather substrate is not particularly limited. Specifically, for example, a grain-side resin layer containing a polymer elastomer such as polyurethane or a (meth) acrylic polymer elastomer is formed by a dry surfacing method or a direct coating method. The dry noodle making method comprises the following steps: a coating liquid containing a colored resin for forming a skin-like layer of grain side is applied to a release sheet and then dried to form a coating film, and the coating film is bonded to the surface of an artificial leather substrate via an adhesive layer, and then the release sheet is released. In addition, the direct coating method is a method of: the resin liquid for forming the grain layer is directly applied to the surface of the artificial leather substrate by a roll coater or a spray coater, and then dried to form the grain layer. According to the direct coating method, a thin grain coating film can be formed as a grain layer. The thickness of such a grain-side coating film is preferably 10 to 1000 μm, and more preferably 30 to 300 μm.
This makes it possible to obtain grain-finished artificial leather according to the present embodiment. The grain-side artificial leather of the present embodiment preferably has an apparent density of 0.60 to 0.85g/cm from the viewpoint of obtaining a high fullness 3 More preferably 0.65 to 0.80g/cm 3 . Further, the grain-finished artificial leather of the present embodiment has both flexibility and a high fullness as those of natural leather. Specifically, for example, the softness measured by the softness tester is preferably 3.5mm or more, more preferably 4.0mm or more in the case of a thickness of 0.5mm, preferably 3.0mm or more in the case of a thickness of 0.7mm, preferably 2.5mm or more in the case of a thickness of 1mm, preferably 3.0mm or more in the case of a thickness of 1.0mm, and preferably 2.0mm or more in the case of a thickness of 1.5 mm.
By using the artificial leather substrate of the present embodiment, it is possible to obtain grain-finished artificial leather having both flexibility and a feeling of fullness, forming fine wrinkles by rounding when bent, and having excellent surface flatness. Such grain-finished artificial leather is used for various applications requiring high-grade feeling, such as shoes, bags, interior decoration, wall decoration, and miscellaneous goods.
Examples
The present invention will be further specifically described below with reference to examples. It should be noted that the scope of the present invention is not limited in any way by the examples.
[ example 1]
Manufacture of artificial leather base material
Water-soluble thermoplastic polyvinyl alcohol (PVA) was used as the sea component, and isophthalic acid-modified polyethylene terephthalate (IPA6-PET) having a modification degree of 6 mol% was used as the island component. PVA and IPA6-PET were supplied to a plurality of spinning nozzles having nozzle temperatures of 260 ℃ and arranged in parallel, and a molten strand was discharged from a spinning nozzle capable of forming a cross section of island components having a uniform cross section of 200 distributed in sea components. At this time, the island component/sea component was supplied at 70/30 with the pressure being adjusted so that the mass ratio of the sea component to the island component was set.
Then, the molten strand was sucked and drawn by a suction apparatus so that the average spinning speed was 3700 m/min, thereby spinning a long fiber of a sea-island type composite fiber having an average fineness of 3.3 dtex. The long fibers of the sea-island type composite fiber spun were continuously stacked on a movable web, and then lightly pressed with a 42 ℃ metal roll to suppress surface fuzzing. Then, the long fibers of the piled sea-island type composite fibers peeled from the web were passed between a corrugated metal roll having a surface temperature of 55 ℃ and a back roll, and hot-pressed at a line pressure of 200N/mm. Thus, a weight per unit area of 31g/m was obtained 2 The web of (1).
The resulting web was laminated with 12 layers using a laminating apparatus so that the total weight per unit area was 330g/m 2 After spraying the anti-breakage oil, a needle having 1 hook with a distance of 3.2mm from the tip of the needle to the first hook (harb) was used, and 3500 punctures/cm was alternately formed from both sides at a needle depth of 10mm 2 The needling is performed under the conditions of (1). The area shrinkage of the web obtained by the needle punching treatment was 68%. Thus, a weight per unit area of 600g/m was obtained 2 The cohesion net of (1).
Then, the band-wound web was passed at a take-up line speed of 10 m/min at 70 ℃ and 50% RH humidity for 30 seconds to be heat-shrunk. The area shrinkage of the entangled web due to the wet heat shrinkage treatment was 47%. Then, the cohesive web was impregnated with the water-dispersed polyurethane (emulsion) and then dried at 150 ℃. The polyurethane emulsion contained 21 mass% of a water-dispersed amorphous polycarbonate/ether-based polyurethane having a 100% modulus of 2.5MPa and a glass transition temperature of-25 ℃ in terms of solid content, and 1.5 mass% of sodium sulfate. Then, the polyurethane-coated entangled web was repeatedly subjected to dipping and sandwiching treatment in hot water at 95 ℃ to dissolve and remove PVA as a sea component. Then, the sheet was dried at 120 ℃ to prepare a 1 st intermediate sheet comprising a nonwoven fabric in which fiber bundles comprising 200 ultrafine fibers having an average fineness of 0.015dtex were three-dimensionally entangled.
Then, the 1 st intermediate body sheet is finished into a 2 nd intermediate body sheet by polishing the surface thereof. The 2 nd intermediate sheet comprises 85 mass% of the ultrafine long fibers and 15 mass% of the polyurethane, and has a basis weight of 680g/m 2 And an apparent density of 0.60g/cm 3 The sheet of (1).
Next, an acrylic polymer elastomer as a 2 nd polymer elastomer, calcium carbonate having a mohs hardness of 3, and a plasticizer were added to the 2 nd intermediate sheet. Specifically, an aqueous dispersion containing 30 mass% of calcium carbonate (Mohs hardness 3), 10 mass% of an acrylic polymer elastomer, and 4 mass% of a fatty acid ester which is liquid at 23 ℃ and has 20 to 50 carbon atoms as a main component was prepared. The average particle size of calcium carbonate was 2.5 μm. The 100% modulus of the acrylic polymer elastomer was 0.8MPa, and the glass transition temperature was-17 ℃.
Then, the 2 nd intermediate sheet was impregnated with the aqueous dispersion at a liquid absorption rate of 100%, and further dried at 120 ℃ to obtain an artificial leather substrate. The artificial leather substrate comprises 59 mass% of nonwoven fabric, 10.5 mass% of polyurethane, 7 mass% of acrylic polymer elastomer, 21 mass% of calcium carbonate, and 2.5 mass% of fatty acid ester.
Then, the artificial leather base material was subjected to a shrinkage processing treatment for shrinking by 5.0% in the longitudinal direction (longitudinal direction). The shrinkage processing was performed by using a shrinkage processing device (a pre-shrinking finishing machine, manufactured by Seiko iron works Co., Ltd.) in which the drum temperature of the shrinkage part was set to 120 ℃, the drum temperature of the heat setting part was set to 120 ℃, and the carrying speed was set to 10 m/min. The thickness of the artificial leather substrate after the shrinking treatment was 1.4mm, and the basis weight was 1035g/m 2 The apparent density is 0.74g/cm 3 . The apparent density of each component in the artificial leather substrate after the shrinkage treatment was 0.44g/cm for the very fine fiber nonwoven fabric as a fabric 3 The polyurethane content was 0.08g/cm 3 The acrylic polymer elastomer was 0.05g/cm 3 Calcium carbonate of 0.16g/cm 3 Fatty acid ester is 0.019g/cm 3 . The total of the apparent densities of the acrylic polymer elastomer and calcium carbonate was 0.21g/cm 3 . The proportion of the (meth) acrylic polymer elastomer was 25% by mass relative to the total of the calcium carbonate and the (meth) acrylic polymer elastomer.
The shore C hardness, hardness and thickness were determined by the following methods. The Shore C hardness is 63, the hardness is 2.8mm, and the thickness is 1.4 mm. And the product of hardness, Shore C hardness and thickness is 247mm 2 。
(Shore C hardness)
Measured according to JIS K7312. Specifically, the shore C hardness of the surface of the artificial leather substrate on the side where the grain layer was formed was measured using a shore C durometer (manufactured by polymer instruments).
(hardness of hardness)
The hardness was measured using a softness tester (leather softness measuring apparatus ST 300: manufactured by MSA Engineering System, Inc., UK). Specifically, after a given ring having a diameter of 25mm was fixed to the lower holder of the apparatus, grain-finished artificial leather was placed on the lower holder. Then, a metal needle having a diameter of 5mm fixed to the upper bar was pressed down against the artificial leather substrate. Then, the upper lever is pressed down, and the value at the time of stopping the upper lever is read. The numerical values indicate the depth of invasion, and larger numerical values indicate more flexibility.
(thickness)
The thickness of the artificial leather substrate was measured according to JIS L1096A method.
Production of grain artificial leather
Grain-coated artificial leathers were obtained by forming a grain-coated film on the surface of the artificial leather substrate after the shrinkage treatment by a direct coating method. In particular, the use of a reverse coater after the shrinking processThe surface of the leather substrate is coated with a polyurethane solution and dried, thereby forming a primer layer. The undercoat layer was adjusted to have a water absorption time of about 3 minutes or more when 3mL of water droplets were added dropwise, that is, a film thickness of about 10 μm. Next, a resin liquid for forming a skin intermediate layer containing a pigment, polyurethane, and an acrylic polymer elastomer was applied to the surface of the primer layer, thereby forming a skin top coat layer having a film thickness of 30 μm. Then, a skin top coat layer having a film thickness of 30 μm was formed on the surface of the skin intermediate layer, thereby obtaining grain-finished artificial leather. The top coat of the epidermis was formed by spray coating a varnish adjusted to 30cp with a rock-field cup (IWATA NK-212 s). Thus, a thickness of 1.45mm and a weight per unit area of 1075g/m were obtained 2 0.74g/m in apparent density 2 The grain-surface artificial leather.
Evaluation of grained Artificial leather
The properties of the grain-finished artificial leather obtained were evaluated as follows.
(drape/feel)
A sample of grain-finished artificial leather cut into 20X 20cm was prepared. Then, the appearance when the surface was curved inward with the center portion as a boundary and the appearance when the surface was grasped were determined according to the following criteria.
A: the bending is curved with a circular arc, and dense and fine wrinkles are generated.
B: the rubber has a strong hand feeling and a strong rebound feeling, or a remarkably low solid feeling, and generates rough wrinkles when bent.
C: the hand was hard and a dead fold was produced when bent.
(flatness)
Samples of grain-finished artificial leather cut to 20X 20cm were prepared. Then, the grain surface was observed, and the degree of surface unevenness was determined according to the following criteria.
A: has less unevenness, excellent flatness, and high glossiness and high quality.
B: the unevenness is conspicuous and the sense of high-quality is poor.
(apparent Density)
The thickness (mm) and the weight per unit area (g/cm) were measured in accordance with JIS L1913 2 ) And calculating apparent densities based on these valuesDegree (g/cm) 2 )。
The evaluation results are shown in table 1 below.
TABLE 1
Figure BDA0002229749810000161
[ example 2]
Polyethylene (PE) was used as the sea component and 6-nylon (6Ny) was used as the island component. PE and 6Ny are supplied to a plurality of spinning nozzles, respectively, and are ejected from spinning nozzles, the nozzle temperature of the plurality of spinning nozzles is set to 260 ℃, and spinning nozzles are arranged in parallel, and the spinning nozzles can form a cross section in which island components with 200 uniform cross sections are distributed in sea components. At this time, the supply was performed while adjusting the pressure so that the mass ratio of the sea component to the island component was 50/50.
Then, the molten fiber was sucked and drawn by a suction device so that the average spinning speed was 3700 m/min, and thereby a long fiber of a sea-island type composite fiber having a fineness of 2.5dtex was spun. The long fibers of the sea-island type composite fiber spun were continuously stacked on a movable web and lightly pressed with a 42 ℃ metal roll in order to suppress surface fuzzing. Then, the long fibers of the sea-island type composite fiber were peeled off from the web, and passed between a corrugated metal roll having a surface temperature of 55 ℃ and a back roll. Thus, hot pressing was carried out at a line pressure of 200N/mm to obtain a weight per unit area of 34g/m 2 The long fiber web of (1).
Next, the resulting web was laminated with 12 layers using a laminating apparatus so that the total weight per unit area was 400g/m 2 And then the needle-breaking-preventing oil agent is sprayed. Next, a needle having 1 hook with a distance of 3.2mm from the tip of the needle to the first hook (harb) was used, and 2500 punches/cm were alternately used from both sides at a needle depth of 10mm 2 And (5) performing needling. The area shrinkage by the needling treatment was 75%, and the weight per unit area of the knitted entangled web was 540g/m 2 . The cohesive net is heat-treated at 140 ℃ and then pressed to smooth the surface so that the specific gravity of the cohesive non-woven fabric is 0.33g/cm 3 。
Then, polyether/ester polyurethane as a 1 st polymer elastomer, which had a 100% modulus of 8.0MPa, a glass transition temperature of-22 ℃ and a solid content of 15 mass% dissolved in N-Dimethylformamide (DMF), and calcium carbonate having a mohs hardness of 3 and an average particle diameter of 2.5 μm were mixed at a solid content ratio of 57/43, impregnated into the entangled nonwoven fabric, solidified in a mixed solution of DMF and water, and then washed with hot water. Then, PE, which is a sea component in the sea-island type composite fiber, was extracted and removed with hot toluene, and dried at 140 ℃ to prepare a 1 st intermediate sheet comprising a nonwoven fabric in which fiber bundles comprising 200 ultrafine fibers having a fineness of 0.01dtex are three-dimensionally entangled.
Then, the 1 st intermediate body sheet is finished into a 2 nd intermediate body sheet by subjecting the surface thereof to a polishing treatment. Then, an aqueous dispersion containing the same acrylic polymer elastomer and plasticizer as used in example 1 was impregnated into the 2 nd intermediate sheet at a liquid absorption rate of 100%, and further, the sheet was dried at 120 ℃ and subjected to a shrinking treatment to obtain an artificial leather substrate having a composition shown in table 2.
Grain-side artificial leathers were obtained and evaluated in the same manner as in example 1, except that the artificial leather substrate was used instead of the artificial leather substrate obtained in example 1. The results are shown in Table 1.
[ examples 3 to 7]
Grain-finished artificial leathers were obtained and evaluated in the same manner as in example 1 or example 2, except that the compositions of the components in example 1 were changed as shown in table 1. The results are shown in Table 1.
Comparative example 1
An artificial leather substrate was obtained and evaluated in the same manner as in example 1, except that calcium carbonate was not added. In addition, grain-finished artificial leathers were obtained and evaluated in the same manner as in example 1. The results are shown in Table 2.
TABLE 2
Figure BDA0002229749810000181
Comparative example 2
An artificial leather substrate was obtained and evaluated in the same manner as in example 1, except that no acrylic polymer elastomer was added. In addition, grain-finished artificial leathers were obtained and evaluated in the same manner as in example 1. The results are shown in Table 2.
Comparative example 3
An artificial leather substrate was obtained and evaluated in the same manner as in example 1, except that silica was used instead of calcium carbonate and no plasticizer was added. In addition, grain-finished artificial leathers were obtained and evaluated in the same manner as in example 1. The results are shown in Table 2.
Comparative example 4
An artificial leather substrate was obtained and evaluated in the same manner as in example 1, except that the alumina shown in table 2 was used instead of the calcium carbonate and the mass ratio was changed to that shown in table 2. In addition, grain-finished artificial leathers were obtained and evaluated in the same manner as in example 1. The results are shown in Table 2.
Comparative example 5
An artificial leather substrate was obtained and evaluated in the same manner as in example 2, except that the acrylic polymer elastomer was not used and the calcium carbonate was changed to the mass ratio shown in table 2. In addition, grain-finished artificial leathers were obtained and evaluated in the same manner as in example 1. The results are shown in Table 2.
Comparative example 6
Grain-finished artificial leather was obtained and evaluated in the same manner as in example 1, except that the composition of each component in example 1 was changed as shown in table 2. The results are shown in Table 1.
The product of hardness, Shore C hardness and thickness is 200-400 mm 2 The grain-side artificial leathers obtained in examples 1 to 7 had a soft hand feeling, were excellent in a full-bodied feeling, had fine wrinkles, had few surface irregularities, were excellent in a plane feeling, had gloss, and were excellent in a high-grade feeling. On the other hand, in comparative examples 1 to 4, the product of the hardness by hardness, the Shore C hardness and the thickness was less than 200mm 2 . Without addition of Mohs hardnessThe grain-finished artificial leather obtained in comparative example 1 having fine particles of degree 4 or less had insufficient fullness, and had poor wrinkles and surface flatness. In addition, the grain-finished artificial leather obtained in comparative example 2, to which no acrylic polymer elastomer was added, had a fullness and poor wrinkles. In addition, comparative example 3, which used silica having a mohs hardness of more than 4 as fine particles and no plasticizer added, had a hard texture and formed deep and coarse wrinkles. In addition, comparative example 4 using large fine particles having a mohs hardness of more than 4 had a hard hand, formed deep and rough wrinkles, and had poor surface flatness. In addition, the product of the hardness, the Shore C hardness and the thickness is 200-400 mm 2 However, comparative example 5, which does not contain the acrylic polymer elastomer and contains a small amount of fine particles, is insufficient in the feeling of fullness and is also poor in wrinkles and surface flatness.
Industrial applicability
The artificial leather substrate of the present invention can be used for the production of grain-finished artificial leather having a soft texture, a smooth surface, fine wrinkles, and a feeling of fullness similar to those of natural leather, and such grain-finished artificial leather can be preferably used for shoes, bags, clothes, gloves, interior trims, vehicle interior trims, conveyor interior trims, building interior trims, and the like.

Claims (14)

1. An artificial leather substrate comprising: a nonwoven fabric, and a polymer elastomer, fine particles and a plasticizer impregnated into the nonwoven fabric,
the polymer elastomer comprises a (meth) acrylic polymer elastomer and polyurethane,
the fine particles comprise at least 1 kind of fine particles selected from gypsum, calcium sulfate, amber, aluminum silicate, magnesium hydroxide, aluminum hydroxide, calcium carbonate, magnesium carbonate and magnesium oxide with Mohs hardness of below 4,
the product of the hardness of the artificial leather base material, the Shore C hardness and the thickness of the artificial leather base material is 200-400 mm 2 。
2. The artificial leather substrate according to claim 1, comprising 15 to 40 mass% of the microparticles.
3. The artificial leather substrate according to claim 1, which comprises 15 to 40 mass% of the polymeric elastomer.
4. The artificial leather substrate according to claim 1, which comprises 0.5 to 5 mass% of the plasticizer.
5. The artificial leather substrate according to claim 1, which comprises 25 to 69.5 mass% of the nonwoven fabric.
6. The artificial leather substrate of claim 1, comprising: 15 to 40 mass% of the polymer elastomer, 15 to 40 mass% of the fine particles, and 0.5 to 5 mass% of the plasticizer.
7. The artificial leather substrate according to any one of claims 1 to 6, wherein the proportion of the (meth) acrylic polymer elastomer is 5 to 50% by mass relative to the total of the fine particles and the (meth) acrylic polymer elastomer.
8. The artificial leather substrate according to any one of claims 1 to 6, wherein the total of the apparent density of the fine particles and the apparent density of the (meth) acrylic polymer elastomer is 0.15 to 0.4g/cm 3 。
9. The artificial leather substrate according to any one of claims 1 to 6, wherein the microparticles comprise at least 1 selected from calcium carbonate and aluminum hydroxide.
10. The artificial leather substrate according to any one of claims 1 to 6, wherein the nonwoven fabric comprises a nonwoven fabric of fibers having an average fineness of 0.7dtex or less.
11. The artificial leather substrate of claim 10, wherein the fibers are polyamide-based fibers.
12. A grain-sized artificial leather comprising: the artificial leather substrate according to any one of claims 1 to 11, and a grain-side resin layer formed on at least one side of the artificial leather substrate.
13. The grain-faced artificial leather according to claim 12, wherein the thickness of the grain-faced resin layer is 30 to 300 μm.
14. The grain-faced artificial leather according to claim 12 or 13, wherein the grain-faced resin layer is a coating film.
CN201880024689.8A 2017-05-01 2018-04-24 Artificial leather substrate and grain-surface artificial leather Active CN110520568B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2017-091274 2017-05-01
JP2017091274 2017-05-01
PCT/JP2018/016625 WO2018203494A1 (en) 2017-05-01 2018-04-24 Artificial leather base material and grained artificial leather

Publications (2)

Publication Number Publication Date
CN110520568A CN110520568A (en) 2019-11-29
CN110520568B true CN110520568B (en) 2022-09-20

Family

ID=64016112

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880024689.8A Active CN110520568B (en) 2017-05-01 2018-04-24 Artificial leather substrate and grain-surface artificial leather

Country Status (7)

Country Link
US (1) US20200071880A1 (en)
EP (1) EP3620572B1 (en)
JP (1) JP7148502B2 (en)
KR (1) KR102578961B1 (en)
CN (1) CN110520568B (en)
TW (1) TWI793119B (en)
WO (1) WO2018203494A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113227489B (en) * 2018-12-27 2023-06-06 株式会社可乐丽 Vertical wool artificial leather and manufacturing method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1823188A (en) * 2003-07-18 2006-08-23 东丽株式会社 Micro staple fiber nonwoven fabric and leather-like article in sheet form, and method for their production
CN101115878A (en) * 2004-12-24 2008-01-30 冈本株式会社 Synthetic resin leather
JP2015124444A (en) * 2013-12-25 2015-07-06 株式会社クラレ Leather-like sheet and method for producing the same
CN105862445A (en) * 2016-06-01 2016-08-17 苏州瑞高新材料有限公司 Method for manufacturing environment-friendly TPU foamed synthetic leather
CN106120361A (en) * 2016-08-30 2016-11-16 苏州瑞高新材料有限公司 A kind of TPU foaming synthetic leather

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5016401B1 (en) * 1970-07-09 1975-06-12
JPS55128078A (en) * 1979-03-26 1980-10-03 Suzutora Seisen Koujiyo Kk Production of synthetic leather like substrate fabric
JPS60181370A (en) * 1984-02-24 1985-09-17 Kanebo Ltd Artificial leather having sterilizing property
JP2002302879A (en) * 2001-04-05 2002-10-18 Kuraray Co Ltd Leathery sheet
JP2003089986A (en) * 2001-09-19 2003-03-28 Kuraray Co Ltd Flame-retardant grained artificial leather and method for producing the same
TW200409783A (en) * 2002-12-11 2004-06-16 Ming Hsing Leather Co Ltd Leather for sports ware with nano structure and method for producing the same
EP1623063B1 (en) * 2003-02-04 2010-11-24 Dow Corning Corporation Coating compositions and textile fabrics coated therewith
DE102005004299A1 (en) * 2005-01-28 2006-08-03 Basf Ag Treating flexible substrates, useful to prepare e.g. fabrics, comprises coating outer surface with a mixture containing organic polymer and inorganic/organic nanoparticular material, optionally fixing and treating with acidic substance
JP2012117154A (en) 2010-11-29 2012-06-21 Kuraray Co Ltd Leather-like sheet excellent in air permeability and method for producing the leather-like sheet
TWI484079B (en) * 2011-09-16 2015-05-11 Jade Long John Entpr Co Ltd The method of making the leather felt weaving cloth and the woven fabric made by the method
JP6473412B2 (en) 2013-02-27 2019-02-20 株式会社クラレ Artificial leather base material, silver-tone artificial leather, method for manufacturing artificial leather base material, and modifier for artificial leather base material
JP6221538B2 (en) * 2013-09-13 2017-11-01 東レ株式会社 Sheet material and method for producing the same
JP6520709B2 (en) * 2013-11-21 2019-05-29 東レ株式会社 Sheet-like material
JP6346873B2 (en) * 2015-06-08 2018-06-20 株式会社クラレ Artificial leather
KR102553348B1 (en) * 2015-09-30 2023-07-07 스미토모 긴조쿠 고잔 가부시키가이샤 Infrared absorbing fine particles, dispersion using the same, dispersion, laminated transparent substrate, film, glass, and manufacturing method thereof
CN107460741A (en) * 2017-09-27 2017-12-12 东莞智国新材料科技有限公司 The preparation method and product of a kind of composite artificial leather

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1823188A (en) * 2003-07-18 2006-08-23 东丽株式会社 Micro staple fiber nonwoven fabric and leather-like article in sheet form, and method for their production
CN101115878A (en) * 2004-12-24 2008-01-30 冈本株式会社 Synthetic resin leather
JP2015124444A (en) * 2013-12-25 2015-07-06 株式会社クラレ Leather-like sheet and method for producing the same
CN105862445A (en) * 2016-06-01 2016-08-17 苏州瑞高新材料有限公司 Method for manufacturing environment-friendly TPU foamed synthetic leather
CN106120361A (en) * 2016-08-30 2016-11-16 苏州瑞高新材料有限公司 A kind of TPU foaming synthetic leather

Also Published As

Publication number Publication date
KR20190139846A (en) 2019-12-18
WO2018203494A1 (en) 2018-11-08
EP3620572B1 (en) 2023-11-29
EP3620572A4 (en) 2020-09-23
CN110520568A (en) 2019-11-29
JPWO2018203494A1 (en) 2020-03-12
JP7148502B2 (en) 2022-10-05
TWI793119B (en) 2023-02-21
EP3620572A1 (en) 2020-03-11
KR102578961B1 (en) 2023-09-14
TW201843374A (en) 2018-12-16
US20200071880A1 (en) 2020-03-05

Similar Documents

Publication Publication Date Title
CN109072543B (en) Grain-surface artificial leather
JP5555468B2 (en) Brushed artificial leather with good pilling resistance
TWI447281B (en) Substrate for artificial leather and process for manufacturing it
JP6429790B2 (en) Nubuck leather-like sheet and method for producing the same
CN110520568B (en) Artificial leather substrate and grain-surface artificial leather
TW201040352A (en) Artificial leather, long fiber entangled web and method for producing the same
CN110520567B (en) Grain-faced artificial leather and method for producing grain-faced artificial leather
TWI467074B (en) Leather-like sheet and method for producing the same
JP5959394B2 (en) Artificial leather with silver
JP2008057098A (en) Napped sheet and method for producing the same
JP6752712B2 (en) Suede-like artificial leather and its manufacturing method
JP2012067397A (en) Grained leather-like sheet

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant