WO2017120718A1 - 一种聚氨酯合成皮革及其制备方法 - Google Patents

一种聚氨酯合成皮革及其制备方法 Download PDF

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Publication number
WO2017120718A1
WO2017120718A1 PCT/CN2016/070554 CN2016070554W WO2017120718A1 WO 2017120718 A1 WO2017120718 A1 WO 2017120718A1 CN 2016070554 W CN2016070554 W CN 2016070554W WO 2017120718 A1 WO2017120718 A1 WO 2017120718A1
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synthetic leather
polyurethane synthetic
adhesive layer
layer
powder
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PCT/CN2016/070554
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English (en)
French (fr)
Inventor
任志军
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鹤山市新科达企业有限公司
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Priority to CN201680001352.6A priority Critical patent/CN106414842B/zh
Priority to PCT/CN2016/070554 priority patent/WO2017120718A1/zh
Publication of WO2017120718A1 publication Critical patent/WO2017120718A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • D06N3/145—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 two or more layers of polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • 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
    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • 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
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • 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
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
    • 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
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/068—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
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1685—Wear resistance
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Definitions

  • the invention relates to the technical field of leather materials, in particular to a polyurethane synthetic leather and a preparation method thereof.
  • Negative ions are increasingly being valued by scientists for improving people's living environment. Air negative ions are referred to as "air vitamins” or "longevity”, and the number of negative ions that maintain people's health is 1000-2000/cm 3 . People who live and work in modern air-conditioned buildings for a long time often feel bored, lethargic, fatigue, nausea, headache, dizziness, work efficiency and physical health. Research shows that the cause of this phenomenon is in the air. The concentration of negative ions is closely related.
  • the object of the present invention is to provide a natural release of negative ions and a fresh odor of plants, so that the amount of ⁇ , ⁇ , ⁇ and X-ray radiation meets domestic and international standards, and the wear resistance and scratch resistance are improved.
  • the technical scheme of the polyurethane synthetic leather of the present invention is as follows:
  • a polyurethane synthetic leather comprising a top layer, an adhesive layer and a substrate, the top layer being formed by coating and drying a surface layer working fluid, the adhesive layer bonding the top layer and the substrate
  • the adhesive layer is coated on the surface layer by coating with an adhesive layer working fluid, and the substrate is bonded and dried on the working layer of the adhesive layer; the surface layer Negative ion powder is added to the working fluid and/or the adhesive layer working fluid.
  • an anion powder is added to the surface layer working fluid.
  • the negative ion powder comprises a plant anion powder and a mineral anion powder; the plant anion powder is prepared by carbonizing the herb at 300-500 ° C and then grinding it into a powder.
  • the formulation of the top layer working fluid is as follows:
  • the negative ion powder comprises >0-2 parts by mass of plant anion powder and 2-2.8 parts by mass of mineral anion powder.
  • >0-2 parts by mass means that the interval of 0-2 parts by mass excludes the endpoint of 0, and the end point of 2 can be taken, that is, (>0)-2 mass parts; the same reason >2-4.8 mass parts means 2-4.8 mass
  • the interval of the interval excludes the endpoint of 2, and the endpoint of 4.8 can be taken, that is, (>2)-4.8 mass parts.
  • the above wear-resistant auxiliary agent is preferably a silicone oil-based wear-resistant auxiliary.
  • the formulation of the adhesive layer working fluid is as follows:
  • DMF dimethylformamide
  • EA is ethyl acetate
  • MEK is methyl ethyl ketone
  • a preparation method of polyurethane synthetic leather comprising the following steps,
  • the post-treatment comprising one or more surface finishes of color correction, embossing, printing and crepe.
  • the working layer of the top layer described in S1 is prepared by diluting the polyurethane resin with a mixture of DMF and EA having a mass ratio of 2:5, and adding a negative ion powder having a mass of 4-5% by mass of the polyurethane resin while stirring at a high speed,
  • the surface auxiliaries of 1-2% of the amount of polyurethane resin, the wear-resistant auxiliaries of 1-2% by mass of polyurethane resin and the 0-10% of the mass of polyurethane resin, the speed of the mixer is 1200r /min or more; after mixing, it is filtered with a 100 mesh filter, and then left to stand for 4-12 hours for defoaming to prepare a surface working solution.
  • the existing polyurethane synthetic leather does not add other solid fillers in the dry surface layer except for the addition of the toner, so the existing polyurethane synthetic leather cannot release negative ions into the air.
  • the invention adds mineral anion powder and plant anion powder into the surface layer of the polyurethane synthetic leather dry method, so that the polyurethane synthetic leather reaches the natural and sustained release of a large amount of negative ions.
  • the negative ion powder on the market is generally composed of tourmaline powder and lanthanide or rare earth metal elements in a certain proportion (usually mass ratio of 35:65), but most of the lanthanides and rare earth metals are radioactive, if the amount of radiation Exceeding the national standard (1.0 ⁇ Sv), it will cause harm to the human body and the environment; while the plant negative ion powder used in the present invention has a certain amount of negative ion release, and the radiation amount of ⁇ , ⁇ , ⁇ and X-ray is 0;
  • the addition of mineral anion powder and plant anion powder to the surface layer of the polyurethane synthetic leather dry method can greatly reduce the amount of ⁇ , ⁇ , ⁇ and X-ray radiation of the polyurethane leather (0.7-0.95 ⁇ Sv), so that the obtained product meets the requirements. National and European standards; and the polyurethane synthetic leather has a fresh odor of plants.
  • Adding a surface active agent to the surface working fluid of the polyurethane synthetic leather dry method can continuously release a large amount of negative ions into the air.
  • a polyurethane synthetic leather comprising a top layer, an adhesive layer and a substrate, the top layer being formed by coating and drying a surface layer working fluid, the adhesive layer bonding the top layer and the substrate
  • the adhesive layer is coated on the surface layer by an adhesive layer working fluid coating, and the substrate is bonded and dried on the working layer of the adhesive layer; only the surface
  • the layer working fluid is added with an anion powder.
  • DMF dimethylformamide
  • EA ethyl acetate
  • MEK methyl ethyl ketone
  • the plant negative ion powder is obtained by carbonizing the herb at 300-500 ° C.
  • the powder is made into a powder;
  • the surface-active auxiliary agent is a sodium alkyl sulfonate surfactant;
  • the wear-resistant auxiliary agent is a liquid silicone polymer.
  • the polyurethane synthetic leather is prepared by the following steps:
  • the polyurethane synthetic leather can be directly packaged or post-processed and packaged.
  • the polyurethane synthetic leather can be modified, embossed, printed, embossed, etc. after surface modification; then product packaging.
  • Embodiment 1 different from Embodiment 1,
  • Embodiment 1 different from Embodiment 1,
  • Embodiment 1 different from Embodiment 1,
  • the negative ion powder is added as a filler to the wet polyurethane synthetic leather substrate, and the polyurethane synthetic leather is obtained by a conventional polyurethane leather dry film transfer process.
  • the negative ion powder is added to the dry working layer of the adhesive layer, and the dry working layer of the dry layer is not added with the negative ion powder; the same substrate is bonded, and the obtained polyurethane synthetic leather has wear resistance and resistance.
  • the scratching performance was also improved (1000 rpm without damage and 1000 without damage), but the release of negative ions was significantly reduced to 7000-10000 ions/CC.
  • Comparative Example 1 the negative ion powder was added as a filler to the wet polyurethane synthetic leather substrate, and the conventional polyurethane leather dry film transfer process was used to obtain a low or no release of the negative ion release of the polyurethane synthetic leather, and ⁇ , ⁇ .
  • the amount of gamma and X-ray radiation is very high, above 3.0 ⁇ Sv, which exceeds national standards.
  • the polyurethane synthetic leather of the invention has a fresh odor of plants; the concentration of fresh odor of synthetic leather plants can be adjusted according to customer requirements.
  • the polyurethane synthetic leather of the present invention can naturally release negative ions into the air, and the radiation amounts of ⁇ , ⁇ , ⁇ and X rays conform to national standards and European standards.
  • the polyurethane synthetic leather of the present invention has good physical properties such as abrasion resistance, scratch resistance, hydrolysis resistance, normal temperature resistance, low temperature tortuosity and peel strength.
  • the invention adds negative ion powder into the polyurethane synthetic leather system, breaks through the technical problem that the polyurethane synthetic leather can naturally release a large amount of negative ions into the air; and maintains various physical properties and environmental protection indexes of the polyurethane synthetic leather, which is consistent with Application requirements for most leather products on the market.
  • Negative ions in the air can reduce active oxygen (oxygen free radicals) generated by pollutants, nitrogen oxides, cigarettes, etc. from the atmosphere, reduce the harmful effects of excessive active oxygen on the human body; neutralize positively charged airborne dust without charge After settling, the air is purified.
  • the polyurethane synthetic leather can release a large amount of negative ions naturally and continuously into the air, and can be used to efficiently purify the air if applied to indoors, cars, and the like.
  • the negative ion polyurethane synthetic leather of the invention can also release a natural fresh scent according to the customer's demand, so that the surrounding air is closer to nature.
  • different substrates can be bonded to each other, and negative ion polyurethane synthetic leather products with different physical properties can be produced. They can be widely used in life as luggage leather, shoe leather, sofa leather, automobile leather, wall leather, and the like. All aspects of it.
  • polyurethane synthetic leather does not contain plasticizer, and can be automatically degraded in the natural environment. Non-toxic and harmless substances, friendly to the human body and the environment.
  • the use of polyurethane synthetic leather as a carrier for releasing negative ions is more environmentally advantageous than the selection of PVC artificial leather.

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

Abstract

本发明公开了一种聚氨酯合成皮革及其制备方法，其中聚氨酯合成皮革包括依次连接的面层、粘合层和基材，其制备方法包括如下步骤，S1.在离型纸上涂布添加有负离子粉的面层工作液,烘干形成面层；S2.在面层上涂布粘合层工作液，然后加温，贴合基材于粘合层工作液上，整体烘干，使粘合层粘合面层和基材；S3.剥离离型纸即得。制得的聚氨酯合成皮革能自然释放负离子且具有植物清新气味、α、β、γ和X射线辐射量符合国内外标准、耐磨性能与耐刮性能等性能优异。

Description

一种聚氨酯合成皮革及其制备方法 技术领域
本发明涉及皮革材料技术领域，具体涉及一种聚氨酯合成皮革及其制备方法。
背景技术
随着人类文明、生产活动，特别是工业化程度的日益提高，污染也越来越严重，特别是人们渴望优雅的环境，于是各种环保材料、功能材料应运而生。负离子对改善人们的生活环境越来越多受到科学工作者的重视。空气负离子被喻为“空气维生素”或“长生素”，维持人们健康的负离子数为：1000-2000个/cm3。长期在现代化空调建筑物中生活和工作的人们，常常会感觉烦闷、昏睡、乏力、恶心、头疼、眩昏，工作效率及身体健康状况明显下降，研究表明，造成这种现象的原因与空气中负离子的浓度密切相关。
而现有的绝大部分皮革产品中不含负离子，或新研发的皮革产品中的负离子含有量虽然大，却不能自然释放负离子，且存在α、β、γ和X射线的辐射量严重超标，皮革的耐磨性能、耐刮性能差等问题。
发明内容
为解决上述技术问题，本发明的目的在于提供一种能自然释放负离子且具有植物清新气味、使α、β、γ和X射线辐射量符合国内外标准、耐磨性能与耐刮性能得到改善的聚氨酯合成皮革及其制备方法。
本发明的聚氨酯合成皮革的技术方案如下：
一种聚氨酯合成皮革，包括面层、粘合层和基材，所述面层是面层工作液涂布烘干制成的，所述粘合层粘合所述面层和所述基材，所述粘合层是通过粘合层工作液涂布在所述面层上加温，使所述基材贴合在所述粘合层工作液上烘干粘合的；所述面层工作液和/或粘合层工作液中添加有负离子粉。
优选地，所述面层工作液中添加有负离子粉。
优选地，所述负离子粉包括植物负离子粉和矿物负离子粉；所述植物负离子粉是通过将草本植物在300-500℃碳化后，再磨成粉末制成的。
优选地，所述矿物负离子粉是通过电气石粉加入镧系元素或稀土金属元素混合而成的。可以进一步按照一定比例混合而成，如电气石粉：(镧系元素或稀土金属元素)＝35:65(质量比)。
优选地，所述面层工作液的配方如下：
Figure PCTCN2016070554-appb-000001
优选地，所述负离子粉包括＞0-2质量份植物负离子粉和2-2.8质量份矿物负离子粉。＞0-2质量份表示0-2质量份的区间排除0的端点，可以取到2的端点，即为(＞0)-2质量份；同理＞2-4.8质量份表示2-4.8质量份的区间排除2的端点，可以取到4.8的端点，即为(＞2)-4.8质量份。上述耐磨助剂优选硅油类耐磨助剂。
优选地，所述粘合层工作液的配方如下：
Figure PCTCN2016070554-appb-000002
上述面层工作液和粘合层工作液的配方中，DMF为二甲基甲酰胺，EA为乙酸乙酯，MEK为甲乙酮。
上述的聚氨酯合成皮革的制备方法，采用的技术方案如下：
一种聚氨酯合成皮革的制备方法，包括如下步骤，
S1.在离型纸上涂布添加有负离子粉的面层工作液,烘干形成面层；
S2.在面层上涂布粘合层工作液，然后加温，贴合基材于粘合层工作液上，整体烘干，使粘合层粘合面层和基材；
S3.剥离离型纸，得到聚氨酯合成皮革。
优选地，还包括S4.直接卷取包装或经过后处理再包装，所述后处理为包括修色、压花、印刷和揉纹中的一种或一种以上的表面修饰。
优选地，S1中所述的面层工作液制备如下：用质量比2:5的DMF和EA混合液稀释聚氨酯树脂，一边高速搅拌一边加入质量占聚氨酯树脂量的4-5％的负离子粉、质量占聚氨酯树脂量的1-2％的表面活性助剂、质量占聚氨酯树脂量的1-2％的耐磨助剂和质量占聚氨酯树脂量的0-10％的色粉，搅拌机转速在1200r/min以上；混合好后，用100目滤网过滤，再静置4-12小时脱泡，制备成面层工作液。
与现有技术相比，本发明的有益效果在于：
①现有的聚氨酯合成革在干法面层中除了添加色粉外，不添加其他固体填料，所以现有的聚氨酯合成革不能向空气中释放负离子。本发明将矿物负离子粉和植物负离子粉加入到聚氨酯合成革干法的面层中，使聚氨酯合成革达到自然、持续释放大量负离子的效果。
②市面上的负离子粉一般为电气石粉和镧系元素或稀土金属元素按照一定比例(通常为质量比35:65)混合而成的，但镧系元素和稀土金属元素大多有放射性，若辐射量超过国家标准(为1.0μSv)，将对人体和环境带来危害；而本发明所使用的植物负离子粉具有一定的负离子释放量，而α、β、γ和X射线的辐射量却为0；将矿物负离子粉和植物负离子粉加入到聚氨酯合成革干法的面层中，可以大大降低聚氨酯皮革的α、β、γ和X射线的辐射量(为0.7-0.95μSv)，使得到的产品符合国家标准和欧洲标准；而且使该聚氨酯合成革具有植物清新气味。
③向聚氨酯合成革干法面层工作液中加入硅油类耐磨助剂，大大提高聚氨酯合成革的耐磨性能和耐刮性能，而且使聚氨酯合成革具有爽滑的手感。
④向聚氨酯合成革干法的面层工作液中加入表面活性助剂，可以使聚氨酯合成革向空气中持续释放大量负离子。
具体实施方式
下面通过具体的实施例对本发明进行详细说明，但这些例举性实施方式的用途和目的仅用来例举本发明，并非对本发明的实际保护范围构成任何形式的任何限定，更非将本发明的保护范围局限于此。
实施例1
一种聚氨酯合成皮革，包括面层、粘合层和基材，所述面层是面层工作液涂布烘干制成的，所述粘合层粘合所述面层和所述基材，所述粘合层是通过粘合层工作液涂布在所述面层上加温，使所述基材贴合在所述粘合层工作液上烘干粘合的；仅所述面层工作液添加有负离子粉。
1)面层工作液的配方如下表1：
表1：面层工作液配方
Figure PCTCN2016070554-appb-000003
2)粘合层工作液的配方如下表2：
表2：粘合层工作液配方
耐水解干法粘合层聚氨酯树脂 100KG
DMF 20KG
EA或MEK 50KG
色粉 1KG
上述面层工作液和粘合层工作液的配方中，DMF为二甲基甲酰胺，EA为乙酸乙酯，MEK为甲乙酮；所述植物负离子粉是通过将草本植物在300-500℃碳化后，再磨成粉末制成的；所述矿物负离子粉是通过电气石粉加入镧系元素或稀土金属元素混合而成的，可以按照一定比例混合而成，如电气石粉：(镧系元素或稀土金属元素)＝35:65(质量比)。所述表面活性助剂为烷基磺酸钠表面活性剂；所述耐磨助剂为液态有机硅聚合物。
具体通过如下步骤制备聚氨酯合成皮革：
①用DMF和EA混合液稀释耐水解干法的面层聚氨酯树脂，一边高速搅拌一边加入植物负离子粉或矿物负离子粉、表面活性助剂、耐磨助剂及色粉，配制成干法的面层工作液；搅拌机转速要在1200r/min以上，负离子粉和色粉才可以更好的分散。干法的面层工作液充分混合好后，用100目滤网过滤除去粒径大的固体,以免造成合成革面有颗粒。再静置4-12小时脱泡，以免造成合成革面有缩孔。
②将干法的面层工作液涂布在离型纸上，烘干后再涂布耐水解粘合层工作液，然后贴合耐水解的基材(因客户需要或实际需求，可以贴合超纤基材，湿法耐水解聚氨酯合成革基材等等)。待烘干后，剥离聚氨酯合成革和离型纸，分别卷取放置待用。根据客户的不同要求，该聚氨酯合成革可以直接包装或经过后处理再包装。
③根据不同的客户要求或实际需求，可以对聚氨酯合成革进行修色、压花、印刷、揉纹等等表面修饰后处理；然后产品包装。
实施例2
参照实施例1，与实施例1不同的是，
1)面层工作液的配方如下表3：
表3：面层工作液配方
Figure PCTCN2016070554-appb-000004
2)粘合层工作液的配方如下表4：
表4：粘合层工作液配方
耐水解干法粘合层聚氨酯树脂 100KG
DMF 20KG
EA或MEK 50KG
色粉 5KG
实施例3
参照实施例1，与实施例1不同的是，
1)面层工作液的配方如下表5：
表5：面层工作液配方
Figure PCTCN2016070554-appb-000005
Figure PCTCN2016070554-appb-000006
2)粘合层工作液的配方如下表6：
表6：粘合层工作液配方
耐水解干法粘合层聚氨酯树脂 100KG
DMF 20KG
EA或MEK 50KG
色粉 10KG
实施例4
参照实施例1，与实施例1不同的是，
2)面层工作液的配方如下表7：
表7：面层工作液配方
耐水解干法粘合层聚氨酯树脂 100KG
DMF 20KG
EA或MEK 50KG
色粉 10KG
2)粘合层工作液的配方如下表8：
表8：粘合层工作液配方
Figure PCTCN2016070554-appb-000007
Figure PCTCN2016070554-appb-000008
对比例1：
将负离子粉作为填充料加入到湿法聚氨酯合成革基材中，使用传统的聚氨酯皮革干法移膜工艺，制得聚氨酯合成革。
将实施例1-4和对比例1制得的聚氨酯合成革进行多次测试，其中实施例1-3制得的聚氨酯合成革的结果数据如下表9：
表9实施例1-3制得的聚氨酯合成革的测试结果
Figure PCTCN2016070554-appb-000009
实施例4的在干法的粘合层工作液中添加负离子粉，干法的面层工作液不添加负离子粉；贴合相同的基材，所制得的聚氨酯合成革的耐磨性能、耐刮性能也是有所提高(1000转无破损和1000次无破损)，但是负离子的释放量明显降低到7000-10000ions/CC。
对比例1的将负离子粉作为填充料加入到湿法聚氨酯合成革基材中，使用传统的聚氨酯皮革干法移膜工艺，制得的聚氨酯合成革负离子释放量低或不释放，而且α、β、γ和X射线的辐射量很高，为3.0μSv以上，超出国家标准。
从而本发明的效果有：
1.本发明的聚氨酯合成皮革具有植物清新气味；能根据客户要求，调节合成革植物清新气味的浓重。
2.本发明的聚氨酯合成皮革能自然向空气中释放负离子，α、β、γ和X射线的辐射量符合国家标准和欧洲标准。
3.本发明的聚氨酯合成皮革具有很好的耐磨性能、耐刮性能、耐水解性能、耐常温和低温曲折性能和剥离强度等物理性能。
4.本发明将负离子粉加入到聚氨酯合成革体系中，突破了聚氨酯合成革能自然、持续向空气中释放大量负离子的技术难题；而且保持了聚氨酯合成革的各项物性指标和环保指标，符合市场上大部分皮革产品的应用要求。
5.空气中的负离子能还原来自大气的污染物质、氮氧化物、香烟等产生的活性氧(氧自由基)，减少过多活性氧对人体的危害；中和带正电的空气飘尘无电荷后沉降，使空气得到净化。该聚氨酯合成革能自然、持续向空气中释放大量负离子，若应用到室内、车内等空间，能起到高效净化空气的作用。
6.本发明的负离子聚氨酯合成革还能根据客户需求，释放出自然清新的气味，使周围的空气更接近大自然。在贴合工序中，贴合不同的基材，可以造出不同物性要求的负离子聚氨酯合成革产品，能作为箱包革、鞋革、沙发革、汽车革、墙面革等等广泛应用到生活中的各个方面。
7.据报道，市面上有能自然释放负离子的聚氯乙烯人造革产品，对比聚氯乙烯人造革，聚氨酯合成革中不添加增塑剂，而且能在自然环境中自动降解成 无毒无害的物质，对人体和环境友好。选用聚氨酯合成革作为释放负离子的载体比选用聚氯乙烯人造革更具有环境优势。
应当理解，这些实施例的用途仅用于说明本发明而非意欲限制本发明的保护范围。此外，也应理解，在阅读了本发明的技术内容之后，本领域技术人员可以对本发明作各种改动、修改和/或变型，所有的这些等价形式同样落于本申请所附权利要求书所限定的保护范围之内。

Claims (10)

  1. 一种聚氨酯合成皮革，其特征在于，包括面层、粘合层和基材，所述面层是面层工作液涂布烘干制成的，所述粘合层粘合所述面层和所述基材，所述粘合层是通过粘合层工作液涂布在所述面层上加温，使所述基材贴合在所述粘合层工作液上烘干粘合的；所述面层工作液和/或粘合层工作液中添加有负离子粉。
  2. 如权利要求1所述的聚氨酯合成皮革，其特征在于，所述面层工作液中添加有负离子粉。
  3. 如权利要求2所述的聚氨酯合成皮革，其特征在于，所述负离子粉包括植物负离子粉和矿物负离子粉；所述植物负离子粉是通过将草本植物在300-500℃碳化后，再磨成粉末制成的。
  4. 如权利要求3所述的聚氨酯合成皮革，其特征在于，所述矿物负离子粉是通过电气石粉加入镧系元素或稀土金属元素混合而成的。
  5. 如权利要求2-4任一所述的聚氨酯合成皮革，其特征在于，所述面层工作液的配方如下：
    Figure PCTCN2016070554-appb-100001
  6. 如权利要求5所述的聚氨酯合成皮革，其特征在于，所述负离子粉包括＞0-2质量份植物负离子粉和2-2.8质量份矿物负离子粉。
  7. 如权利要求2-4任一所述的聚氨酯合成皮革，其特征在于，所述粘合层工作液的配方如下：
    Figure PCTCN2016070554-appb-100002
    Figure PCTCN2016070554-appb-100003
  8. 权利要求2-7任一所述的聚氨酯合成皮革的制备方法，其特征在于，包括如下步骤，
    S1.在离型纸上涂布添加有负离子粉的面层工作液,烘干形成面层；
    S2.在面层上涂布粘合层工作液，然后加温，贴合基材于粘合层工作液上，整体烘干，使粘合层粘合面层和基材；
    S3.剥离离型纸，得到聚氨酯合成皮革。
  9. 如权利要求8所述的聚氨酯合成皮革的制备方法，其特征在于，还包括S4.直接卷取包装或经过后处理再包装，所述后处理为包括修色、压花、印刷和揉纹中的一种或一种以上的表面修饰。
  10. 如权利要求8所述的聚氨酯合成皮革的制备方法，其特征在于，S1中所述的面层工作液制备如下：用质量比2:5的DMF和EA混合液稀释聚氨酯树脂，一边高速搅拌一边加入质量占聚氨酯树脂量的4-5％的负离子粉、质量占聚氨酯树脂量的1-2％的表面活性助剂、质量占聚氨酯树脂量的1-2％的耐磨助剂和质量占聚氨酯树脂量的0-10％的色粉，搅拌机转速在1200r/min以上；混合好后，用100目滤网过滤，再静置4-12小时脱泡，制备成面层工作液。
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