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CN112195654B - Composite non-woven fabric for PU synthetic leather and preparation method thereof - Google Patents

Composite non-woven fabric for PU synthetic leather and preparation method thereof Download PDF

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Publication number
CN112195654B
CN112195654B CN202010944910.0A CN202010944910A CN112195654B CN 112195654 B CN112195654 B CN 112195654B CN 202010944910 A CN202010944910 A CN 202010944910A CN 112195654 B CN112195654 B CN 112195654B
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CN
China
Prior art keywords
woven fabric
antibacterial
synthetic leather
interlayer cloth
antistatic agent
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Application number
CN202010944910.0A
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Chinese (zh)
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CN112195654A (en
Inventor
胡忠杰
葛庆
张丽君
吴城锋
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.)
Jiangsu Huafeng Microfiber Material Co ltd
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Jiangsu Huafeng Microfiber Material Co ltd
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Priority to CN202010944910.0A priority Critical patent/CN112195654B/en
Publication of CN112195654A publication Critical patent/CN112195654A/en
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Publication of CN112195654B publication Critical patent/CN112195654B/en
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    • 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
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/06—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer mechanically connected, e.g. by needling to another layer, e.g. of fibres, of paper
    • 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
    • D06N3/0015—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 fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0025—Rubber threads; Elastomeric fibres; Stretchable, bulked or crimped fibres; Retractable, crimpable fibres; Shrinking or stretching of fibres during manufacture; Obliquely threaded fabrics
    • D06N3/0027—Rubber or elastomeric fibres
    • 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
    • D06N3/0015—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 fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0034—Polyamide fibres
    • 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
    • D06N3/12—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
    • 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
    • D06N3/142—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 mixture of polyurethanes with other resins in the same layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0292—Polyurethane fibres
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • 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
    • D06N2201/10—Conjugate fibres, e.g. core-sheath, side-by-side
    • 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
    • D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The invention relates to a composite non-woven fabric for PU synthetic leather and a preparation method thereof, wherein the method comprises the following steps: (1) Etching the interlayer cloth by adopting a pulse laser beam to obtain the interlayer cloth with the micro-groove structure on the surface; (2) Dipping the interlayer cloth with the micro-groove structure on the surface into finishing liquid containing the antibacterial antistatic agent, and drying to obtain the interlayer cloth containing the antibacterial antistatic agent; (3) And compounding the antibacterial antistatic agent interlayer cloth with a non-woven fabric formed by sea-island fibers by adopting a needling method to prepare the composite non-woven fabric. The PU synthetic leather prepared by dipping the composite non-woven fabric in polyurethane slurry has the bacteriostasis rate of 90.0-99.9% to staphylococcus aureus, 90.0-99.9% to klebsiella pneumoniae and the surface resistance of 1 multiplied by 10 3 ～1×10 6 The method is simple and easy to implement, and the prepared synthetic leather has good and durable antibacterial and antistatic functions.

Description

Composite non-woven fabric for PU synthetic leather and preparation method thereof
Technical Field
The invention belongs to the technical field of synthetic leather, and relates to a composite non-woven fabric for PU synthetic leather and a preparation method thereof.
Background
In the prior art, in order to obtain antibacterial and antistatic effects, the method is generally divided into two modes, namely a melt spinning method and a functional auxiliary agent (such as an antibacterial agent and an antistatic modifier) is added into the synthetic leather to obtain fibers with antibacterial and antistatic effects; the other is to make the fiber into fabric, and then to post-treat the fabric to give the fabric a certain antibacterial and antistatic effect. In addition, there is a technique of combining melt spinning modification and post-treatment.
The antibacterial and antistatic effects given to the fabric by the post-treatment technology are often poor in durability, and at present, the research direction is mainly focused on the dispersion and the distribution of the functional auxiliary agents in the functional treatment liquid and the binding force between the functional auxiliary agents and the fabric; while the antibacterial and antistatic fiber with good durability can be obtained by a melt spinning modification method, the method has high requirements on the selection of functional auxiliary agents and the selection of processes, the addition amount of the functional auxiliary agents is limited by spinnability, and the problems of difficult spinning formation and the like are caused when the functional auxiliary agents are excessively added. For example, in the prior art, carbon element type conductive/antistatic additives such as carbon black/carbon fiber/carbon nano tube are used as antistatic modifier of fiber and dispersed into spinning nylon 6 slices, when the addition amount of the antistatic modifier reaches a certain concentration during melt spinning, the antistatic effect is good, but the spinnability is poor, a spinneret plate is easy to be blocked, defective products such as broken filaments, hard filaments, large filaments and the like appear, and the product quality is affected; when the amount of the antistatic modifier added at the time of melt spinning is small, spinnability is not deteriorated, but the antistatic effect is not ideal.
The prior art also discloses an antibacterial spun-bonded non-woven fabric, which comprises a non-woven fabric surface layer, a non-woven fabric interlayer, a non-woven fabric bottom layer and antibacterial particles positioned in gaps of the non-woven fabric interlayer, wherein the diameter of the antibacterial particles is smaller than the fiber gaps in the non-woven fabric interlayer and larger than the fiber gaps of the non-woven fabric surface layer and the non-woven fabric bottom layer, the antibacterial particles are locked inside the non-woven fabric by utilizing the gap difference of the fabric, and the antibacterial non-woven fabric has certain advantages in the processing mode and the durability of the antibacterial effect. The method has higher requirements on the control of the fiber gaps of the multi-layer non-woven fabric, the particle size selectivity of antibacterial particles is limited, and the structure is not suitable for the preparation of PU synthetic leather, because the fiber gaps of the non-woven fabric made of sea-island fibers can be widened in the splitting process of the PU synthetic leather; if the non-woven fabric made of the sea-island fibers is used as an interlayer, the non-woven fabric with fine fibers is required to be used as a surface layer and a non-woven fabric bottom layer for effectively locking the antibacterial particles, and when the sea-island fibers are opened, the sea-island fibers are wrapped by the non-woven fabric with fine fibers of the surface layer and the bottom layer, so that the opening process is difficult; if the non-woven fabric made of the sea-island fiber is used as a surface layer or a bottom layer, the gaps of the fiber become wider after the fiber is opened, and the antibacterial particles are easy to remove in the fiber opening process.
Therefore, the development of the composite non-woven fabric for PU synthetic leather with excellent spinnability and durable antibacterial and antistatic properties and the preparation method thereof have very important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a composite non-woven fabric for PU synthetic leather and a preparation method thereof.
The invention aims to provide a composite non-woven fabric for PU synthetic leather, which comprises a non-woven fabric composed of sea-island fibers, an interlayer fabric and an antibacterial antistatic agent fixed in a micro groove of the interlayer fabric; the interlayer cloth contains elastic fibers; the non-woven fabric is firmly connected with the interlayer cloth; the PU synthetic leather is prepared from the composite non-woven fabric, the antibacterial rate of the PU synthetic leather on staphylococcus aureus is 90.0-99.9%, the antibacterial rate on klebsiella pneumoniae is 90.0-99.9%, and the surface resistance is 1 multiplied by 10 3 ～1×10 6 Ohm, PU synthetic leather is tested after 20 times of water washing according to AATCC 135-2018 method, the antibacterial rate to staphylococcus aureus is 90.0% -95%, the antibacterial rate to klebsiella pneumoniae is 90.0% -95%, and the surface resistance is 1 multiplied by 10 3 ～1×10 6 Ohm, the tearing strength of PU synthetic leather is 100-130N.
The second purpose of the invention is to provide a preparation method of the composite non-woven fabric for PU synthetic leather, firstly, micro grooves are formed on the surface of the interlayer fabric, so that the antibacterial antistatic agent can be fixed on the interlayer fabric, and the antibacterial antistatic performance of the interlayer fabric is durable; secondly, compounding the interlayer cloth containing the antibacterial antistatic agent and the non-woven fabric formed by the sea-island fibers together by using a needling method to form a structure with fibers intertangled, so that the non-woven fabric formed by the sea-island fibers is not damaged in the fiber opening process of the synthetic leather, and the composite strength of the composite non-woven fabric is ensured; in addition, the invention also adopts a mode of adding spandex into the interlayer cloth to increase the composite strength of the interlayer cloth containing the antibacterial antistatic agent and the non-woven fabric formed by the sea-island fibers so as to further improve the mechanical properties, antibacterial antistatic property and other comprehensive properties of the composite non-woven fabric and the PU synthetic leather prepared by the composite non-woven fabric.
In order to achieve the above purpose, the invention adopts the following scheme:
a composite non-woven fabric for PU synthetic leather comprises non-woven fabric, interlayer cloth and an antibacterial antistatic agent fixed in a micro groove of the interlayer cloth; the interlayer cloth contains elastic fibers; the non-woven fabric is firmly connected with the interlayer cloth; the micro-groove is positioned on one side of the interlayer cloth facing the non-woven fabric; the non-woven fabric is composed of sea-island fibers; the interlining cloth contains elastic fiber.
As a preferable technical scheme:
the composite non-woven fabric for PU synthetic leather is prepared by immersing the composite non-woven fabric in polyurethane slurry, and performing solidification, water washing, fiber opening, sheet skin grinding, dyeing and water washing and drying;
the PU synthetic leather prepared by the composite non-woven fabric has the bacteriostasis rate of 90.0-99.9% to staphylococcus aureus, 90.0-99.9% to klebsiella pneumoniae and the surface resistance of 1 multiplied by 10 3 ～1×10 6 Ohmic;
the PU synthetic leather prepared by the composite non-woven fabric is tested after being washed for 20 times according to the AATCC 135-2018 method, the antibacterial rate of the PU synthetic leather on staphylococcus aureus is 90.0% -95.0%, the antibacterial rate on klebsiella pneumoniae is 90.0% -95.0%, and the surface resistance is 1 multiplied by 10 3 ～1×10 6 Ohmic;
the tearing strength of the PU synthetic leather (before washing) prepared by the composite non-woven fabric is 100-130N.
The composite non-woven fabric for PU synthetic leather is characterized in that the elastic fiber is spandex.
In the composite nonwoven fabric for PU synthetic leather, in the sea-island fiber, the sea component is LDPE (low density polyethylene PE) (melt-spun polymer which can be removed by solvent), and the island component is nylon PA or polyester PET (melt-spun polymer which can not be removed by solvent which dissolves the sea component); the volume ratio of the island component to the sea component is 70-80:30-20; the number of fixed islands in the sea-island fiber is 16-64; preferably 37 to 64;
when the volume ratio of the island component to the sea component is smaller than 70:30, the firm connection between the non-woven fabric and the interlayer cloth is insufficient, and when the volume ratio of the island component to the sea component is larger than 80:20, island combination is easy, and spinning is difficult; the number of fixed islands is less than 16, which leads to insufficient connection strength between the subsequent non-woven fabric and the interlayer fabric, particularly affects the composite strength of the composite fabric, preferably, the number of fiber islands is more than 37, the composite strength is optimal, and excessive island numbers lead to poor dyeability caused by too thin fibers.
In the needling process, the existence of elastic fibers is beneficial to the firm connection of the non-woven fabric and the interlayer cloth, so that the prepared composite non-woven fabric still has tight adhesion with the interlayer cloth after the fiber opening treatment, and the interlayer cloth is not easily damaged by the impact force generated by a high-strength needling machine due to the spandex.
The composite non-woven fabric for PU synthetic leather has the spandex content of 5-15 wt% in the interlayer fabric; the rest components are the same materials as the island components; the firm connection is achieved by needling. When the spandex content in the interlayer cloth is less than 5wt%, the lifting non-woven fabric and the interlayer cloth are firmly connected; when the spandex content in the interlayer cloth is more than 15wt%, the elasticity is too high, which is not beneficial to firmly connecting the non-woven fabric and the interlayer cloth.
The composite non-woven fabric for PU synthetic leather is characterized in that the interlayer cloth is woven fabric; the width of the micro groove is 200-500 μm, and the depth is 200-500 μm. The woven fabric is of a regular fabric structure, so that when the non-woven fabric is prepared in the needling process, the non-woven fabric and the interlayer fabric only generate a longitudinal (needling direction) regular cross relation, and the influence of the interlayer fabric on sea-island fibers in the non-woven fabric in the subsequent fiber opening process is reduced to the greatest extent.
The micro-grooves are favorable for the adhesion of the silver-based antibacterial and antistatic auxiliary agent, the width of the micro-grooves is less than 200 mu m, the depth of the micro-grooves is less than 200 mu m, the adhesion amount of the silver-based antibacterial and antistatic auxiliary agent is insufficient, the antistatic property and the antibacterial property cannot meet the requirements, the width of the micro-grooves is more than 500 mu m, the depth of the micro-grooves is more than 500 mu m, the fiber strength is greatly reduced, and the interlayer cloth is easy to be broken when the non-woven fabric is needled.
The composite non-woven fabric for PU synthetic leather has the median diameter D50 of 5-50 mu m; the antibacterial antistatic agent is silver powder or silver-coated copper powder. The D50 is less than 5 mu m, the antibacterial antistatic agent is not easy to form a continuous phase in the polyacrylic acid grafting modified polyurethane solution, and the antibacterial antistatic effect can not meet the requirement; the D50 is more than 50 mu m, the antibacterial antistatic agent is easy to settle in the polyacrylic acid grafting modified polyurethane solution, so that the concentration of the silver antibacterial antistatic auxiliary agent is uneven, and the antibacterial antistatic effect is unstable.
The invention also provides a preparation method of the composite non-woven fabric for PU synthetic leather, which is used for preparing the composite non-woven fabric for PU synthetic leather, and comprises the following steps:
(1) Etching one side of the interlayer cloth by adopting a pulse laser beam to obtain the interlayer cloth with a micro-groove structure on one side; compared with other technologies such as micro-grooves, plasmas and the like, the micro-grooves formed by the method have more uniform width and depth, so that the auxiliary agent is uniformly dispersed in the micro-grooves to form an ordered structure, and the antibacterial antistatic agent can be orderly and continuously arranged along the direction of the micro-grooves to form a conductive path;
(2) Dipping the interlayer cloth with the micro-groove structure on one side into finishing liquid containing the antibacterial antistatic agent, and drying, crosslinking and curing to obtain the interlayer cloth containing the antibacterial antistatic agent;
(3) An interlayer cloth containing an antibacterial antistatic agent is used as a bottom cloth, and a non-woven fabric consisting of sea-island fibers is used as an upper cloth; compounding the interlayer cloth containing the antibacterial antistatic agent and the non-woven fabric formed by the sea-island fibers by adopting a needling method to prepare a compound non-woven fabric; wherein, the side with micro-grooves of the interlayer cloth containing the antibacterial antistatic agent faces the non-woven fabric.
In the preparation of the sea-island fiber, the draft multiple is 1-5 times, and the draft temperature is 50-80 ℃; preferably, the draft multiple is 3-5 times, the draft temperature is 50-70 ℃, and then the nonwoven fabric is dried, shaped, curled, cut off and packaged for manufacturing and using; the needle punching process can entangle sea-island fiber with fiber in the sandwich cloth to form double-layer structure, and the composite structure has the structure characteristic of sea-island fiber maintained and no influence in the splitting process of synthetic leather, so that the synthetic leather has excellent mechanical performance and may be used in producing antibacterial and antistatic performance. The needling density of the needling machine adopted in the needling method is 200-300 times/cm < 2 >, the needle depths are 8-10 mm, 6-8 mm, 4-6 mm, 2-4 mm,0mm and the vehicle speed is 2-3 m/min in sequence.
As a preferable technical scheme:
the preparation method of the composite non-woven fabric for PU synthetic leather comprises the following steps that in the step (1), the energy of a pulse laser beam is 100-500 MW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Etching the pulse laser beam along a linear track;
in the step (2), the configuration process of the finishing liquid comprises the following steps: adding an antibacterial antistatic agent into the polyacrylic acid grafting modified polyurethane solution, and uniformly stirring; the stirring speed is 500-1000 rpm, and the stirring time is 0.5-2 hours; the liquid carrying rate of the sandwich cloth with the micro-groove structure on one side after impregnation is 40-60 wt%, and the drying and crosslinking temperature is 80-140 ℃, preferably 110-140 ℃.
The preparation method of the composite non-woven fabric for PU synthetic leather comprises the steps that in finishing liquid, the mass concentration of an antibacterial antistatic agent is 0.1-5%, preferably 0.1-2.0%; the mass concentration of the polyacrylic acid grafted modified polyurethane is 20-30%, wherein the grafting rate of the polyacrylic acid is 5-10%, and the solvent is deionized water. The mass concentration of the antibacterial antistatic agent is less than 0.1%, the adhesion amount of the antibacterial antistatic auxiliary agent is insufficient, and the antistatic property and the antibacterial property can not meet the requirements; the mass concentration of the polyacrylic acid grafted modified polyurethane is less than 20%, the grafting rate of the polyacrylic acid is less than 5%, the adhesiveness is not strong, the antibacterial and antistatic effects are not durable, and if the mass concentration of the polyacrylic acid grafted modified polyurethane is more than 30%, the grafting rate of the polyacrylic acid is more than 10%, the fiber strength is greatly reduced, and the interlayer cloth is easy to be broken when the non-woven fabric is needled.
The principle of the invention is as follows:
before the interlayer cloth is compounded with the non-woven fabric, antibacterial antistatic agents are fixed in the micro-groove structure on the surface of the interlayer cloth; the micro-groove structure can enable the antibacterial antistatic agent to be stably fixed on the interlayer cloth, so that the excellent and durable antibacterial and antistatic performance of the PU synthetic leather is ensured. Compared with the antibacterial antistatic fiber prepared by the conventional spinning modification method, the method has no spinnability problem, and can prepare the fiber with high-concentration antibacterial antistatic additive content; compared with the modification by the conventional post-treatment method, the antibacterial and antistatic auxiliary agent is orderly arranged along the groove direction, so that a conductive path is easier to form, the conventional fabric is immersed, and the antibacterial and antistatic auxiliary agent is in a disordered distribution state on the surface of the fabric, so that the effect is often poor; the antibacterial antistatic agent added in the invention can not be separated out in the subsequent treatment and use processes; the conductive path is formed along the fiber direction more easily, and compared with the post-treatment method, the additive addition amount required under the condition of reaching the same antistatic grade is less; compared with the method of blending yarn which is influenced by the addition amount of the auxiliary agent to spinnability, the method can be used for preparing synthetic leather with higher antibacterial property and antistatic property grade and smaller surface resistance.
In order to ensure the mechanical property of the composite non-woven fabric, the invention takes the woven antibacterial antistatic interlayer cloth as the base cloth in the preparation process of the composite non-woven fabric, and the non-woven fabric formed by sea-island fibers is compounded on the base cloth by a needling method, and the fibers of the two layers are intertwined with each other. Among them, the mechanical properties are good because: the process of removing sea components through an organic solvent to obtain superfine fibers after PU of the nonwoven fabric made of sea island fibers is immersed and solidified is called as fiber opening, for a multi-layer nonwoven fabric structure, covering other fiber layers on the surface of the sea island fibers tends to block the fiber opening process of the sea island fibers at the later stage to a certain extent, so that the fiber opening efficiency is influenced, and when the woven antibacterial antistatic sandwich fabric is used as a base fabric, the regular fabric structure ensures that the nonwoven fabric and the sandwich fabric only generate fiber entanglement in the needling direction during the preparation of the composite nonwoven fabric in the needling process, the subsequent fiber opening resistance is not caused, the tight covering of other fiber layers on the surface of the sea island fibers caused by excessive entanglement is avoided, so that the fiber opening difficulty is caused, and the retention of the strength of the superfine fibers is ensured. The stable and durable antibacterial and antistatic property is due to the following reasons: the interlayer cloth contains elastic fibers, so that firm connection between the interlayer cloth and the non-woven fabric is facilitated in the needling process, and the composite strength of the interlayer cloth and the non-woven fabric is further improved; even after the sea-island fibers in the non-woven fabric are opened, the interlayer cloth and the superfine fibers separated from the sea phase still have good composite strength; if the interlayer cloth is separated from the non-woven fabric formed by the sea-island fibers in the fiber opening process, the interlayer cloth cannot disperse acting force on the non-woven fabric under the action of external force, and the interlayer cloth is poor in mechanical property after being subjected to antibacterial and antistatic modification, so that the interlayer cloth becomes a breaking point of the action of the external force, and the performance of the whole PU leather is deteriorated.
Advantageous effects
(1) According to the preparation method of the composite non-woven fabric for PU synthetic leather, the micro grooves are formed on the surface of the interlayer fabric, so that the antibacterial antistatic agent can be fixed on the interlayer fabric, and the antibacterial antistatic performance of the interlayer fabric is durable; secondly, compounding the antibacterial antistatic interlayer cloth and the sea-island fiber layer together by using a needling method to form a structure with fibers intertangled, and further, the invention also adopts a mode of adding spandex into the interlayer cloth to increase the composite strength of the antibacterial antistatic interlayer cloth and the sea-island fiber layer so as to ensure the mechanical property and antibacterial antistatic property of the PU synthetic leather; the woven interlayer cloth is used, and the composite non-woven fabric prepared from the woven interlayer cloth does not influence the follow-up opening process of the sea-island fiber;
(2) The invention relates to a composite non-woven fabric for PU synthetic leather, which has the antibacterial rate of 90.0-99.9% to staphylococcus aureus, 90.0-99.9% to klebsiella pneumoniae and 1X 10 surface resistance 3 ～1×10 6 Ohm, and the PU synthetic leather is tested after 20 times of water washing according to AATCC 135-2018 method, the antibacterial rate to staphylococcus aureus is90.0 to 95 percent, the bacteriostasis rate to klebsiella pneumoniae is 90.0 to 95 percent, and the surface resistance is 1 multiplied by 10 3 ～1×10 6 Ohm, the tearing strength of PU synthetic leather is 100-130N.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The test method adopted by the invention is as follows:
(1) Antibacterial test: performing antibacterial rate test of testing staphylococcus aureus and klebsiella pneumoniae on the PU synthetic leather by adopting a standard ASTM E2149-13a method;
(2) Antistatic test: testing the surface resistance value of the PU synthetic leather by adopting a standard GB/T24249-2009 method;
(3) Antibacterial, antistatic persistence test: after washing PU synthetic leather for 20 times by adopting a washing method of AATCC 135-2018, respectively testing the antibacterial property and the antistatic property of the PU synthetic leather according to the ASTM E2149-13a and the GB/T24249-2009 method;
(4) Tear strength test criteria: the tear strength of PU synthetic leather was tested using standard ISO 3377-1:2011.
The woven cloth used in the examples was purchased from the commercial product of Minghung textile;
the polyacrylic acid graft modified polyurethane used in the examples was purchased from commercial products of Guangzhou Henry, new Material Co., ltd;
the silver-coated copper powder used in the examples was purchased from silver peak metal technologies, inc. In guangzhou;
silver powder used in the examples was purchased from south palace sharp alloy welding materials limited.
In all the following examples and comparative examples, the process of preparing the PU synthetic leather from the composite nonwoven fabric comprises the following steps: immersing the composite non-woven fabric in polyurethane slurry, solidifying, washing (washing is washing DMF solvent brought by PU), opening (opening is extracting LDPE with toluene at 80 ℃), peeling, grinding, dyeing and washing and drying to obtain PU synthetic leather; the thickness of the prepared PU synthetic leather is 1.2mm.
Example 1
The preparation method of the composite non-woven fabric for the PU synthetic leather comprises the following steps:
(1) Etching one side of a woven fabric (70D nylon (PA 6) and 40D spandex are blended according to the mass ratio of 9:1) by adopting a pulse laser beam to obtain sandwich fabric with a micro-groove structure on one side; wherein the energy of the pulse laser beam is 100MW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The width of the micro groove is 200 μm, and the depth is 200 μm;
(2) Preparing finishing liquid: adding an antibacterial antistatic agent (silver-coated copper powder with a median particle diameter D50 of 5 mu m) into the polyacrylic acid grafting modified polyurethane solution, and uniformly stirring to obtain finishing liquid; wherein the stirring speed is 500 rpm, and the stirring time is 1 hour; in the finishing liquid, the mass concentration of the antibacterial antistatic agent is 0.1%; the mass concentration of the polyacrylic acid grafting modified polyurethane solution is 20%, wherein the grafting rate of the polyacrylic acid is 5%, and the solvent is deionized water;
(3) Dipping the interlayer cloth with the micro-groove structure on one side into finishing liquid containing an antibacterial antistatic agent, and drying to obtain the interlayer cloth containing the antibacterial antistatic agent; wherein, the liquid carrying rate of the dipping is 40wt percent, and the drying temperature is 110 ℃;
(4) Compounding the antibacterial antistatic agent interlayer cloth and the non-woven fabric formed by the sea-island fibers by adopting a needling method to prepare a compound non-woven fabric; wherein, the side with micro-grooves of the interlayer cloth containing the antibacterial antistatic agent faces the non-woven fabric; in the sea-island fiber, the sea component is LDPE, and the island component is PA6; the volume ratio of the island component to the sea component is 70:30; in the preparation process of the sea-island fiber, the draft multiple is 3 times, the draft temperature is 50 ℃, and the number of the fibers in the island component is 37;
the needle density of the needling machine adopted in the needling method is 200 times/cm 2 The needle depths are 8mm,6mm,4mm,2mm,0mm in sequence, and the vehicle speed is 2m/min;
the prepared composite non-woven fabric comprises non-woven fabric composed of sea-island fibers, interlayer cloth and an antibacterial antistatic agent fixed in a micro groove of the interlayer cloth; the non-woven fabric is firmly connected with the interlayer cloth;
the PU synthetic leather prepared by the composite non-woven fabric has the bacteriostasis rate of 90.2% to staphylococcus aureus, 90.5% to klebsiella pneumoniae and 1×10 surface resistance 6 Ohm, tearing strength 130N, PU synthetic leather is tested after 20 times of water washing according to AATCC 135-2018 method, the antibacterial rate to staphylococcus aureus is 90%, the antibacterial rate to klebsiella pneumoniae is 90.1%, and the surface resistance is 1 multiplied by 10 6 Ohmic.
Comparative example 1
The preparation method of the composite non-woven fabric for PU synthetic leather has the steps basically same as those of the example 1, and the difference is that the woven fabric in the step (1) is prepared by blending 70D nylon (PA 6)/40D spandex in a mass ratio of 9.7:0.3; preparing the obtained composite non-woven fabric into PU synthetic leather; the performance index of the PU synthetic leather is shown in table 1.
Comparative example 2
The procedure of the preparation method of the composite nonwoven fabric for PU synthetic leather is basically the same as that of the example 1, except that the antibacterial antistatic agent in the step (2) is silver-coated copper powder with the median diameter D50 of 2 mu m; preparing the obtained composite non-woven fabric into PU synthetic leather; the performance index of the PU synthetic leather is shown in table 1.
Comparative example 3
The procedure of the preparation method of the composite non-woven fabric for PU synthetic leather is basically the same as that of the example 1, except that the step (1) is not performed, namely, the interlayer cloth in the step (3) does not contain micro grooves; preparing the obtained composite non-woven fabric into PU synthetic leather; the performance index of the PU synthetic leather is shown in table 1.
TABLE 1
Performance index Unit (B) Example 1 Comparative example 1 Comparative example 2 Comparative example 3
Antibacterial rate of staphylococcus aureus ％ 90.2 90.3 90.1 86.4
Antibacterial rate of klebsiella pneumoniae ％ 90.5 90.6 90.5 87.9
Surface resistance Ohm-meter 1×10 6 1×10 6 3×10 7 2×10 8
Tear strength N 130 85 135 142
Antibacterial ratio of staphylococcus aureus tested after water washing ％ 90.0 90 90.1 78.4
Antibacterial ratio of klebsiella pneumoniae tested after water washing ％ 90.1 90.2 90.3 77.9
Surface resistance after washing Ohm-meter 1×10 6 1×10 6 3×10 7 8×10 9
As can be seen from comparing comparative example 1 with example 1, the tearing strength of the PU synthetic leather prepared in comparative example 1 is significantly lower than that of example 1, because the spandex content of the woven fabric in comparative example 1 is very low, and the presence of the spandex is favorable for firmly connecting the nonwoven fabric with the interlayer fabric during the needling process, so that the prepared composite nonwoven fabric still has tight adhesion between the nonwoven fabric and the interlayer fabric after the fiber opening treatment, and the interlayer fabric is not easily damaged by the impact force generated by a high-strength needling machine due to the presence of the spandex. When the spandex content in the interlayer cloth is too small, the effect of firmly connecting the lifting non-woven fabric and the woven fabric layer is not great.
As can be seen from comparing comparative example 2 with example 1, the PU synthetic leather prepared in comparative example 2 has significantly higher surface resistance than example 1 because the median particle diameter of the antibacterial antistatic agent used in comparative example 2 is too small, and when the finishing liquid containing the antibacterial antistatic agent is used to impregnate woven cloth, the dispersion distribution of the antibacterial antistatic agent in the micro grooves is poor, and a continuous phase is not easily formed, resulting in unsatisfactory antibacterial antistatic effect.
As can be seen from comparing comparative example 3 with example 1, the PU synthetic leather prepared in comparative example 3 is poor in antistatic and antibacterial effects, and slightly reduced in antibacterial and antistatic durability. Because the fiber is not grooved in the comparative example 3, the mechanical properties of the fiber are slightly higher than those of the embodiment 1, but the antistatic effect is poor because the antistatic effect is usually realized only by regularly arranging antistatic additives to form conductive paths, the surface of the composite non-woven fabric prepared in the comparative example 3 does not contain a micro-groove structure, the antistatic additives enriched on the surface of the composite non-woven fabric are irregular and are unfavorable for forming the conductive paths, and the antibacterial antistatic additives in the embodiment 1 are orderly arranged along the groove direction and are easier to form the conductive paths, so the surface resistance of the comparative example 3 is higher and the antistatic effect is weakened; the reason for the reduced antibacterial effect is: when finishing with finishing liquid with the same concentration, the grooves can load relatively more auxiliary agents, so that the antibacterial effect in the embodiment 1 is better; in addition, the antibacterial and antistatic durability of comparative example 3 is slightly reduced because the auxiliary agent is concentrated on the surface of the fabric, and the combination property with the fabric is relatively poor compared with the method of example 1 using slot filling, and the antibacterial and antistatic effect is slightly reduced after multiple times of washing.
Example 2
The preparation method of the composite non-woven fabric for the PU synthetic leather comprises the following steps:
(1) Etching one side of a woven fabric (70D nylon (PA 66) and 40D spandex are blended according to the mass ratio of 9.5:0.5) by adopting a pulse laser beam to obtain sandwich fabric with a micro-groove structure on one side; wherein the pulseThe energy of the laser beam was 200MW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The width of the micro groove is 250 μm, and the depth is 250 μm;
(2) Preparing finishing liquid: adding an antibacterial antistatic agent (silver powder with the median particle diameter D50 of 10 mu m) into the polyacrylic acid grafting modified polyurethane solution, and uniformly stirring to obtain finishing liquid; wherein the stirring speed is 600 rpm, and the stirring time is 1 hour; in the finishing liquid, the mass concentration of the antibacterial antistatic agent is 0.5%; the mass concentration of the polyacrylic acid grafting modified polyurethane solution is 22%, wherein the grafting rate of the polyacrylic acid is 6%, and the solvent is deionized water;
(3) Dipping the interlayer cloth with the micro-groove structure on one side into finishing liquid containing an antibacterial antistatic agent, and drying to obtain the interlayer cloth containing the antibacterial antistatic agent; wherein, the liquid carrying rate of the dipping is 45 weight percent, and the drying temperature is 120 ℃;
(4) Compounding the antibacterial antistatic agent interlayer cloth and the non-woven fabric formed by the sea-island fibers by adopting a needling method to prepare a compound non-woven fabric; wherein, the side with micro-grooves of the interlayer cloth containing the antibacterial antistatic agent faces the non-woven fabric; in the sea-island fiber, the sea component is LDPE, and the island component is PA66; the volume ratio of the island component to the sea component is 80:20; in the preparation process of the sea-island fiber, the draft multiple is 1 time, the draft temperature is 60 ℃, and the number of the fibers in the island component is 16;
the needling density of the needling machine adopted in the needling method is 220 times/cm 2 The needle depths are 8mm,6mm,4mm,2mm,0mm in sequence, and the vehicle speed is 2.5m/min;
the prepared composite non-woven fabric comprises non-woven fabric composed of sea-island fibers, interlayer cloth and an antibacterial antistatic agent fixed in a micro groove of the interlayer cloth; the non-woven fabric is firmly connected with the interlayer cloth;
the PU synthetic leather prepared by the composite non-woven fabric has the bacteriostasis rate of 95% on staphylococcus aureus, 94.8% on klebsiella pneumoniae and the surface resistance of 1 multiplied by 10 5 Ohm, tear strength 121N, PU synthetic leather tested after 20 times of water washing according to AATCC 135-2018 method, the antibacterial rate to staphylococcus aureus is 93.6%, the antibacterial rate to klebsiella pneumoniae is 92.5%, and the surface resistance is 1 multiplied by 10 5 Ohmic.
Example 3
The preparation method of the composite non-woven fabric for the PU synthetic leather comprises the following steps:
(1) Etching one side of a woven fabric (70D nylon (PA 6) and 40D spandex are blended according to the mass ratio of 9.4:0.6) by adopting a pulse laser beam to obtain sandwich fabric with a micro-groove structure on one side; wherein the energy of the pulse laser beam is 230MW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The width of the micro groove is 310 μm, and the depth is 360 μm;
(2) Preparing finishing liquid: adding an antibacterial antistatic agent (silver powder with a median particle diameter D50 of 25 mu m) into the polyacrylic acid grafting modified polyurethane solution, and uniformly stirring to obtain finishing liquid; wherein the stirring speed is 750 rpm, and the stirring time is 0.5 hours; in the finishing liquid, the mass concentration of the antibacterial antistatic agent is 1%; the mass concentration of the polyacrylic acid grafting modified polyurethane solution is 24%, wherein the grafting rate of the polyacrylic acid is 7%, and the solvent is deionized water;
(3) Dipping the interlayer cloth with the micro-groove structure on one side into finishing liquid containing an antibacterial antistatic agent, and drying to obtain the interlayer cloth containing the antibacterial antistatic agent; wherein, the liquid carrying rate of the dipping is 50wt percent, and the drying temperature is 80 ℃;
(4) Compounding the antibacterial antistatic agent interlayer cloth and the non-woven fabric formed by the sea-island fibers by adopting a needling method to prepare a compound non-woven fabric; wherein, the side with micro-grooves of the interlayer cloth containing the antibacterial antistatic agent faces the non-woven fabric; in the sea-island fiber, the sea component is LDPE, and the island component is PA6; the volume ratio of the island component to the sea component is 75:25; in the preparation process of the sea-island fiber, the draft multiple is 5 times, the draft temperature is 80 ℃, and the number of the fibers in the island component is 55;
the needle density of the needle machine adopted in the needling method is 250 times/cm 2 The needle depths are 8mm,6mm,4mm,2mm,0mm in sequence, and the vehicle speed is 2m/min;
the prepared composite non-woven fabric comprises non-woven fabric composed of sea-island fibers, interlayer cloth and an antibacterial antistatic agent fixed in a micro groove of the interlayer cloth; the non-woven fabric is firmly connected with the interlayer cloth;
PU synthetic leather prepared from the composite non-woven fabric is golden yellowThe antibacterial rate of staphylococcus chromogenes is 99.9%, the antibacterial rate of klebsiella pneumoniae is 99.9%, and the surface resistance is 1×10 3 Ohm, tear strength 109N, PU synthetic leather tested after 20 times of water washing according to AATCC 135-2018 method, the antibacterial rate to staphylococcus aureus is 94.9%, the antibacterial rate to klebsiella pneumoniae is 94.8%, and the surface resistance is 1 multiplied by 10 3 Ohmic.
Example 4
The preparation method of the composite non-woven fabric for the PU synthetic leather comprises the following steps:
(1) Etching one side of a woven fabric (70D nylon (PA 46) and 40D spandex are blended according to the mass ratio of 9.2:0.8) by adopting a pulse laser beam to obtain sandwich fabric with a micro-groove structure on one side; wherein the energy of the pulse laser beam is 350MW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The width of the micro groove is 370 μm, and the depth is 420 μm;
(2) Preparing finishing liquid: adding an antibacterial antistatic agent (silver powder with a median particle diameter D50 of 35 mu m) into the polyacrylic acid grafting modified polyurethane solution, and uniformly stirring to obtain finishing liquid; wherein the stirring speed is 850 revolutions per minute, and the stirring time is 1.5 hours; in the finishing liquid, the mass concentration of the antibacterial antistatic agent is 1.5%; the mass concentration of the polyacrylic acid grafting modified polyurethane solution is 26%, wherein the grafting rate of the polyacrylic acid is 8%, and the solvent is deionized water;
(3) Dipping the interlayer cloth with the micro-groove structure on one side into finishing liquid containing an antibacterial antistatic agent, and drying to obtain the interlayer cloth containing the antibacterial antistatic agent; wherein, the liquid carrying rate of the dipping is 55wt percent, and the drying temperature is 110 ℃;
(4) Compounding the antibacterial antistatic agent interlayer cloth and the non-woven fabric formed by the sea-island fibers by adopting a needling method to prepare a compound non-woven fabric; wherein, the side with micro-grooves of the interlayer cloth containing the antibacterial antistatic agent faces the non-woven fabric; in the sea-island fiber, the sea component is LDPE, and the island component is PA46; the volume ratio of the island component to the sea component is 70:30; in the preparation process of the sea-island fiber, the draft multiple is 2 times, the draft temperature is 55 ℃, and the number of the fibers in the island component is 64;
the needling density of the needling machine adopted in the needling method is 230 times/cm 2 The needle depths are 8mm,6mm,4mm,2mm,0mm in sequence, and the vehicle speed is 3m/min;
the prepared composite non-woven fabric comprises non-woven fabric composed of sea-island fibers, interlayer cloth and an antibacterial antistatic agent fixed in a micro groove of the interlayer cloth; the non-woven fabric is firmly connected with the interlayer cloth;
the PU synthetic leather prepared by the composite non-woven fabric has the bacteriostasis rate of 96.2% to staphylococcus aureus, 97% to klebsiella pneumoniae and 1×10 surface resistance 6 Ohm, tear strength is 101N, PU synthetic leather is tested after 20 times of water washing according to AATCC 135-2018 method, the antibacterial rate to staphylococcus aureus is 95%, the antibacterial rate to klebsiella pneumoniae is 92.2%, and the surface resistance is 1 multiplied by 10 6 Ohmic.
Example 5
The preparation method of the composite non-woven fabric for the PU synthetic leather comprises the following steps:
(1) Etching one side of a woven fabric (70D nylon (PA 66) and 40D spandex are blended according to the mass ratio of 0.85:0.15) by adopting a pulse laser beam to obtain sandwich fabric with a micro-groove structure on one side; wherein the energy of the pulse laser beam is 450MW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The width of the micro groove is 450 μm, and the depth is 500 μm;
(2) Preparing finishing liquid: adding an antibacterial antistatic agent (a mixture of silver powder and silver-coated copper powder in a mass ratio of 1:1, wherein the median particle diameter D50 of the mixture is 10 mu m) into a polyacrylic acid grafting modified polyurethane solution, and uniformly stirring to obtain finishing liquid; wherein the stirring speed is 900 revolutions per minute, and the stirring time is 2 hours; in the finishing liquid, the mass concentration of the antibacterial antistatic agent is 2%; the mass concentration of the polyacrylic acid grafting modified polyurethane solution is 28%, wherein the grafting rate of the polyacrylic acid is 9%, and the solvent is deionized water;
(3) Dipping the interlayer cloth with the micro-groove structure on one side into finishing liquid containing an antibacterial antistatic agent, and drying to obtain the interlayer cloth containing the antibacterial antistatic agent; wherein, the liquid carrying rate of the dipping is 45 weight percent, and the drying temperature is 140 ℃;
(4) Compounding the antibacterial antistatic agent interlayer cloth and the non-woven fabric formed by the sea-island fibers by adopting a needling method to prepare a compound non-woven fabric; wherein, the side with micro-grooves of the interlayer cloth containing the antibacterial antistatic agent faces the non-woven fabric; in the sea-island fiber, the sea component is LDPE, and the island component is PA66; the volume ratio of the island component to the sea component is 73:27; in the preparation process of the sea-island fiber, the draft multiple is 4 times, the draft temperature is 75 ℃, and the number of the fibers in the island component is 45;
the needling density of the needling machine adopted in the needling method is 260 times/cm 2 The needle depths are 8mm,6mm,4mm,2mm,0mm in sequence, and the vehicle speed is 3m/min;
the prepared composite non-woven fabric comprises non-woven fabric composed of sea-island fibers, interlayer cloth and an antibacterial antistatic agent fixed in a micro groove of the interlayer cloth; the non-woven fabric is firmly connected with the interlayer cloth;
the PU synthetic leather prepared by the composite non-woven fabric has the bacteriostasis rate of 99.9 percent on staphylococcus aureus, 99.9 percent on klebsiella pneumoniae and 1 multiplied by 10 surface resistance 3 Ohm, tear strength of 112N, after 20 times of washing according to AATCC 135-2018 method, the PU synthetic leather has a bacteriostasis rate of 93.6% to staphylococcus aureus, 92% to klebsiella pneumoniae and a surface resistance of 1X 10 3 Ohmic.
Example 6
The preparation method of the composite non-woven fabric for the PU synthetic leather comprises the following steps:
(1) Etching one side of a woven fabric (70D nylon (PA 10) and 40D spandex are blended according to the mass ratio of 9.1:0.9) by adopting a pulse laser beam to obtain sandwich fabric with a micro-groove structure on one side; wherein the energy of the pulse laser beam is 500MW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The width of the micro groove is 500 μm, and the depth is 250 μm;
(2) Preparing finishing liquid: adding an antibacterial antistatic agent (silver-coated copper powder with the median particle diameter D50 of 50 mu m) into the polyacrylic acid grafting modified polyurethane solution, and uniformly stirring to obtain finishing liquid; wherein the stirring speed is 1000 rpm, and the stirring time is 1.5 hours; in the finishing liquid, the mass concentration of the antibacterial antistatic agent is 5%; the mass concentration of the polyacrylic acid grafting modified polyurethane solution is 30%, wherein the grafting rate of the polyacrylic acid is 10%, and the solvent is deionized water;
(3) Dipping the interlayer cloth with the micro-groove structure on one side into finishing liquid containing an antibacterial antistatic agent, and drying to obtain the interlayer cloth containing the antibacterial antistatic agent; wherein, the liquid carrying rate of the dipping is 60wt percent, and the drying temperature is 135 ℃;
(4) Compounding the antibacterial antistatic agent interlayer cloth and the non-woven fabric formed by the sea-island fibers by adopting a needling method to prepare a compound non-woven fabric; wherein, the side with micro-grooves of the interlayer cloth containing the antibacterial antistatic agent faces the non-woven fabric; in the sea-island fiber, the sea component is LDPE, and the island component is PA10; the volume ratio of the island component to the sea component is 80:20; in the preparation process of the sea-island fiber, the draft multiple is 3 times, the draft temperature is 60 ℃, and the number of the fibers in the island component is 48;
the needle density of the needling machine adopted in the needling method is 280 times/cm 2 The needle depths are 8mm,6mm,4mm,2mm,0mm in sequence, and the vehicle speed is 2.5m/min;
the prepared composite non-woven fabric comprises non-woven fabric composed of sea-island fibers, interlayer cloth and an antibacterial antistatic agent fixed in a micro groove of the interlayer cloth; the non-woven fabric is firmly connected with the interlayer cloth;
the PU synthetic leather prepared by the composite non-woven fabric has the bacteriostasis rate of 97.3 percent on staphylococcus aureus, 98.6 percent on klebsiella pneumoniae and 1 multiplied by 10 surface resistance 4 Ohm, tear strength 114N, PU synthetic leather tested after 20 times of washing according to AATCC 135-2018 method, the antibacterial rate to staphylococcus aureus is 92%, the antibacterial rate to klebsiella pneumoniae is 91.7%, and the surface resistance is 1 multiplied by 10 4 Ohmic.

Claims (4)

1. The preparation method of the composite non-woven fabric for the PU synthetic leather is characterized by comprising the following steps of:
(1) Etching one side of the interlayer cloth by adopting a pulse laser beam to obtain the interlayer cloth with a micro-groove structure on one side;
(2) Dipping the interlayer cloth with the micro-groove structure on one side into finishing liquid containing an antibacterial antistatic agent, and drying to obtain the interlayer cloth containing the antibacterial antistatic agent;
(3) Compounding the interlayer cloth containing the antibacterial antistatic agent and the non-woven fabric formed by the sea-island fibers by adopting a needling method to prepare a compound non-woven fabric; wherein, the side with micro-grooves of the interlayer cloth containing the antibacterial antistatic agent faces the non-woven fabric;
the composite non-woven fabric for the PU synthetic leather comprises non-woven fabric, interlayer cloth and an antibacterial antistatic agent fixed in a micro groove of the interlayer cloth; the non-woven fabric is firmly connected with the interlayer cloth; the micro-groove is positioned on one side of the interlayer cloth facing the non-woven fabric; the non-woven fabric is composed of sea-island fibers; the interlayer cloth contains elastic fibers; the elastic fiber is spandex; in the interlayer cloth, the content of spandex is 5-15wt%; the interlayer cloth is woven cloth; the width of the micro groove is 200-500 μm, and the depth is 200-500 μm;
in the sea-island fiber, the sea component is LDPE, and the island component is PA; the volume ratio of the island component to the sea component is 70:30-80:20; the number of fixed islands in the sea-island fiber is 16-64;
in the interlayer cloth, the rest components are made of the same materials as the island components in the sea-island fiber; the firm connection is realized by a needling method;
the median diameter D50 of the antibacterial antistatic agent is 5-50 mu m; the antibacterial antistatic agent is silver powder and/or silver-coated copper powder.
2. The method for producing a composite nonwoven fabric for PU synthetic leather according to claim 1, wherein in the step (1), the energy of the pulse laser beam is 100 to 500MW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Etching the pulse laser beam along a linear track;
in the step (2), the configuration process of the finishing liquid comprises the following steps: adding an antibacterial antistatic agent into the polyacrylic acid grafting modified polyurethane solution, and uniformly stirring; the stirring speed is 500-1000 rpm, and the stirring time is 0.5-2 hours; the liquid carrying rate of the sandwich cloth with the micro-groove structure on one side after impregnation is 40-60wt% and the drying temperature is 80-140 ℃.
3. The method for preparing the composite non-woven fabric for PU synthetic leather according to claim 2, wherein the mass concentration of the antibacterial antistatic agent in the finishing liquid is 0.1-5%; the mass concentration of the polyacrylic acid grafting modified polyurethane solution is 20-30%, wherein the grafting rate of the polyacrylic acid is 5-10%, and the solvent is deionized water.
4. The method for preparing the composite non-woven fabric for the PU synthetic leather according to claim 1, wherein the PU synthetic leather prepared from the composite non-woven fabric has a bacteriostasis rate of 90.0% -99.9% on staphylococcus aureus, a bacteriostasis rate of 90.0% -99.9% on klebsiella pneumoniae and a surface resistance of 1 multiplied by 10 3 ~1×10 6 Ohmic;
the PU synthetic leather prepared by the composite non-woven fabric is tested after being washed for 20 times according to an AATCC 135-2018 method, the antibacterial rate of the PU synthetic leather on staphylococcus aureus is 90.0% -95.0%, the antibacterial rate on klebsiella pneumoniae is 90.0% -95.0%, and the surface resistance is 1 multiplied by 10 3 ~1×10 6 Ohmic;
the tearing strength of the PU synthetic leather prepared by the composite non-woven fabric is 100-130N.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11247072A (en) * 1998-03-05 1999-09-14 Toray Ind Inc Artificial leather and its production
US6767853B1 (en) * 1999-07-05 2004-07-27 Kuraray Co., Ltd. Fibrous substrate for artificial leather and artificial leather using the same
TWI230216B (en) * 2002-03-11 2005-04-01 San Fang Chemical Industry Co Manufacture method for artificial leather composite reinforced with ultra-fine fiber non-woven fabric
CN1625626A (en) * 2002-02-01 2005-06-08 株式会社可隆 Composite sheet used for artificial leather with low elongation and excellent softness
JP2008121128A (en) * 2006-11-09 2008-05-29 Kuraray Co Ltd Artificial leather and method for producing the same
JP2008231585A (en) * 2007-03-16 2008-10-02 Teijin Fibers Ltd Method for producing moisture-permeable and waterproof fabric, moisture-permeable and waterproof fabric and textile product
CN202072964U (en) * 2011-03-23 2011-12-14 汤为人 Bacteriostatic deodorant ultrafine-fiber artificial leather

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11247072A (en) * 1998-03-05 1999-09-14 Toray Ind Inc Artificial leather and its production
US6767853B1 (en) * 1999-07-05 2004-07-27 Kuraray Co., Ltd. Fibrous substrate for artificial leather and artificial leather using the same
CN1625626A (en) * 2002-02-01 2005-06-08 株式会社可隆 Composite sheet used for artificial leather with low elongation and excellent softness
TWI230216B (en) * 2002-03-11 2005-04-01 San Fang Chemical Industry Co Manufacture method for artificial leather composite reinforced with ultra-fine fiber non-woven fabric
JP2008121128A (en) * 2006-11-09 2008-05-29 Kuraray Co Ltd Artificial leather and method for producing the same
JP2008231585A (en) * 2007-03-16 2008-10-02 Teijin Fibers Ltd Method for producing moisture-permeable and waterproof fabric, moisture-permeable and waterproof fabric and textile product
CN202072964U (en) * 2011-03-23 2011-12-14 汤为人 Bacteriostatic deodorant ultrafine-fiber artificial leather

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