CN102080332A - Preparation method of waterborne polyurethane synthetic leather base - Google Patents

Abstract

The invention relates to a method for manufacturing a water-based polyurethane synthetic leather base. Water-based polyurethane resin uses water as the dispersion medium. It is non-toxic, environmentally friendly, safe and non-flammable. It is the best substitute for solvent-based resins. However, its application in synthetic leather is relatively lagging behind, mainly focusing on the surface finishing of synthetic leather. . The present invention designs base cloth→pretreatment→drying→dipping water-based polyurethane slurry→coating water-based polyurethane foam coating→drying steps to manufacture water-based polyurethane synthetic leather base, and the product has the basic structure of solvent-based wet-process synthetic leather base , the feel and physical properties are close to solvent-based synthetic leather base; no solvent is used for processing in the whole production process; it can be used for post-processing of any synthetic leather products; post-processing is performed using water-based polyurethane materials, which can be used as shoe leather and sofa leather , luggage leather, garment leather, etc.

Description

A kind of manufacture method of waterborne polyurethane synthetic leather bass

technical field

The invention relates to a method for manufacturing a water-based polyurethane synthetic leather base.

Background technique

Solvent-based resins contain a large amount of volatile organic solvents (VOC), which are discharged into the atmosphere during use, which not only damages the environment and endangers human health, but also causes waste of resources and energy. At present, the production and processing of the entire synthetic leather industry is based on the base of solvent-based polyurethane, and a large number of organic solvents are used in the production process, such as dimethyl formamide, methyl ethyl ketone, acetone, toluene, ethyl acetate, etc. These solvents It is extremely harmful to the human body. Generally, the solid content of polyurethane resin for synthetic leather is about 30%, and the organic solvent content reaches 70%, and a certain amount of organic solvent will be added during the processing of synthetic leather, so the amount of organic solvent used in actual production is larger. . Although in recent years, due to the increase in raw material prices and restrictions on environmental protection emissions, companies have to consider the recycling and reuse of solvents. The solvent recycling capacity has reached about 90%, but there are still about 10% of solvents that cannot be recycled. Wastewater is discharged into the environment in the form of waste water, which has caused great harm to the environment and human body.

Water-based polyurethane resin uses water as the dispersion medium, has the advantages of non-toxic, environmental protection, safety, and non-combustibility, and is the best substitute for solvent-based resins. However, the application of water-based polyurethane resin in synthetic leather is relatively lagging behind, mainly focusing on the surface finishing of synthetic leather. Only water-based dry film transfer technology and printing technology are applied in actual production. The base of water-based polyurethane synthetic leather is still only In laboratory development stage.

Contents of the invention

The purpose of the present invention is to provide a kind of manufacture method of water-based polyurethane synthetic leather base, can make the semi-finished product of water-based polyurethane synthetic leather with the non-woven fabric base of similar solvent-based wet coating by adopting water-based polyurethane resin, and it and solvent-based The structure of wet-laid base is similar, but the production process uses more environmentally friendly water-based polyurethane resin to make synthetic leather base.

The technical solution adopted in the present invention is: a method for manufacturing a water-based polyurethane synthetic leather base, which is characterized in that: sequentially comprising the following steps

(a) Preparation of the base fabric: the base fabric is selected from one of non-woven fabrics, woven fabrics or knitted fabrics; b) Pretreatment: the formula ratio of the treatment agent solution is:

Water-soluble polymer: 0-3 parts;

Silicone treatment agent: 1-3 parts;

Water: 100 parts;

The liquid carrying rate of the pretreatment base cloth is 30~100%;

(e) Coating water-based polyurethane foam coating: the formula ratio of water-based polyurethane foam layer slurry is:

Waterborne polyurethane resin: 100 parts;

Foaming agent: 1.5-2 parts;

Foam stabilizer: 2-3 parts;

Thickener: 1-4 parts;

Colorant: 1 part;

Cross-linking agent: 0-3 parts;

Body filler: 1 part;

The density of the foaming slurry is 300~700g/L; the coating amount of the coating liquid per square meter is 100~800g/m ² ;

(f) drying, drying usually adopts infrared heating or microwave drying equipment.

The water-soluble polymer content in the above step (b) is 2-3 parts, and the liquid carrying rate of the pretreated base cloth is 50-80; (e) the density of the foaming slurry in the step is 400-600g/L; The coating amount per square meter is 200~500g/m ² .

The water-soluble polymer in the above step (b) is polyvinyl alcohol, cellulose derivatives, gelatin or modified starch; the silicone treatment agent is amino silicone oil or amino modified silicone oil softener; the water-based polyurethane resin in step (e) is Anionic aliphatic polyester, anionic aliphatic polyether, anionic aliphatic polyester-polyether, anionic aromatic polyester, anionic aromatic polyether or anionic aromatic polyester-polyether; thickening The agent is acrylic thickener, polyurethane thickener or cellulose thickener; the crosslinking agent is isocyanate crosslinking agent or melamine crosslinking agent; the colorant is water-based pigment paste or dye; the foaming agent is Fatty acid salt surfactants, fatty alcohol sulfate surfactants, alkylbenzenesulfonic acid surfactants; foam stabilizers are fatty amide surfactants, ammonium oxide surfactants or cationic surfactants; body fillers are Superfine silica, calcium carbonate powder, superfine natural fur powder, natural feather powder, natural wool powder, natural silk powder or wood cellulose.

The water-soluble polymer in the above step (b) is polyvinyl alcohol; the silicone treatment agent is an amino-modified silicone oil softener; the water-based polyurethane resin in the step (e) is an anionic aliphatic polyester-polyether type and an anionic aromatic poly Ester-polyether type; thickener is acrylic thickener, polyurethane thickener or cellulosic thickener, preferably uses acrylic and polyurethane thickener; Crosslinking agent is isocyanate type crosslinking agent; The coloring agent is a water-based pigment paste or dye, preferably a water-based pigment paste; the foaming agent is a fatty acid salt surfactant and an alkylbenzenesulfonic acid surfactant; the foam stabilizer is a fatty amide surfactant; the body filler is an ultrafine Silica, lignocellulose, calcium carbonate powder or extra fine natural hide powder.

The following two steps are also included between steps (b) and (e) above:

(c) Drying: The drying temperature is 80~160°C;

(d) Immersion water-based polyurethane slurry: water-based polyurethane slurry is obtained by mixing one or more of water-based polyurethane resins, thickeners, cross-linking agents and colorants, and the proportion of the slurry solution formula is:

Waterborne polyurethane resin: 100 parts;

Water: 0-30 parts;

Thickener: 1-4 parts;

Colorant: 1-3 parts;

Cross-linking agent: 0-1 part;

After impregnation, the liquid-carrying rate of the non-woven fabric is 50-60%.

The drying temperature in step (c) above is 130~150°C; the water-based polyurethane resin in step (d) is anionic aliphatic polyester type, anionic aliphatic polyether type, anionic aliphatic polyester-polyether type, anionic aromatic Polyester type, anionic aromatic polyether type or anionic aromatic polyester-polyether type; thickener is acrylic thickener, polyurethane thickener or cellulose thickener; crosslinking agent is isocyanate Type cross-linking agent or melamine type cross-linking agent; coloring agent is water-based pigment paste or dye.

The water-based polyurethane resin in the above step (d) is anionic aliphatic polyester-polyether type and anionic aromatic polyester-polyether type; the thickener is an acrylic or polyurethane thickener; the cross-linking agent is an isocyanate cross-linking agent Joint agent; coloring agent is water-based pigment paste.

The present invention has the following advantages:

The water-based polyurethane synthetic leather base prepared by the present invention has the basic structure of a solvent-based wet-process synthetic leather base, and its feel and physical properties are close to the solvent-based synthetic leather base; no solvent is used for processing in the entire production process; it can be used in any The post-processing of synthetic leather products, such as dry film transfer, printing and spraying, embossing, embossing, surface grinding, etc., especially the post-processing of water-based polyurethane resin materials is more environmentally friendly; the post-processing of water-based polyurethane materials can be used Compared with solvent-based products, no solvent remains in the finished product for making shoe leather, sofa leather, luggage leather, clothing leather, etc., and there is no harm to human health; the process route of the invention is simple, and the price and cost are comparable to solvent-based products. No solvent is used in the process, and there is basically no VOC emission, which not only reduces the investment and use cost of solvent recovery equipment, but also reduces energy waste and environmental pollution.

Detailed ways

The present invention will be described in detail below in conjunction with specific embodiments.

The main equipment involved in the specific embodiment of the present invention includes conventional equipment such as a cloth rack, a cloth storage machine, a dipping tank with pressing rollers, a coating head, an infrared or microwave drying and setting line, and a winder.

Part of product names, purposes and characteristic descriptions used in the specific embodiments of the present invention: Material Grade use characteristic factory non-woven fabric W-1023S120 Bottom fabric PA30/PET70, 1.0mm, 230g/ ^m2 Fujian Nanfang non-woven fabric HS-1028 Bottom fabric High density 1.0mm, 280g/m ² Fujian Nanfang Woven 0.55mmPU leather base cloth Bottom fabric 0.55mm polyester cotton (black gray, wet) single Fujian Nanfang knitted fabric 0.7mm black imitation cashmere Bottom fabric 0.7mm, 180g g/ ^m2 Haining Howard Johnson warp knitting knitted fabric Tricot suede Bottom fabric 50Dx75D 140 g/ ^m2 Wujiang City Wanlong Textile water soluble polymer PVA-117 Base fabric pretreatment polyvinyl alcohol Japanese Kuraray Silicone treatment agent DH-105 Base fabric pretreatment Fiber softener Yantai Daocheng Waterborne polyurethane resin Impranil LP RSC 1380 Dipping anionic aliphatic Germany Bayer Waterborne polyurethane resin DG-6915 Dipping Anionic Aromatic Yantai Daocheng Waterborne polyurethane resin Impranil DLU foam coating anionic aliphatic Germany Bayer Waterborne polyurethane resin DG-6061 foam coating Anionic Aromatic Yantai Daocheng thickener Borching ALA Dip, Foam Coating Acrylic Germany and America thickener DZC-240 Dip, Foam Coating Polyurethane Yantai Daocheng Colorant Dip, Foam Coating Water-based color paste Shiming Technology crosslinking agent Bayhydur 3100 Dip, Foam Coating Isocyanates Germany Bayer Foaming agent Stockal STA foam coating Ammonium stearate Stockhausen, Germany Foam stabilizer Stockal SR foam coating Succinamide salt Stockhausen, Germany Body filler OK 500 foam coating silica Germany Degussa Body filler FD600/30 foam coating Lignocellulosic Reidenmeyer, Germany

Embodiment 1 :

(a) The bottom fabric in the step is W-1023S120 non-woven fabric of Fujian Nanfang Co., Ltd., 1.0mm, 230g/m ² , PA30/PET70;

(b) The formulation of the treatment agent solution in the step is: polyvinyl alcohol 2 copies Fiber softener 1 copy water 100 copies

The liquid carrying rate of the pretreated base cloth is 60%.

(c) The drying temperature in the step is 130°C.

(d) The formula of water-based polyurethane slurry in the step is: Anionic Aliphatic Waterborne Polyurethane 100 copies water 30 copies acrylic thickener 4 parts water-based paint paste 3 copies Isocyanate crosslinking agent 1 copy

After impregnation, the liquid-carrying rate of the non-woven fabric is 60%.

(e) The formula of water-based polyurethane slurry in the step is: Anionic Aliphatic Waterborne Polyurethane 100 copies fatty acid salt surfactant 2 copies Succinamide salt 3 copies acrylic thickener 4 parts water-based paint paste 1 copy Isocyanate crosslinking agent 3 copies Ultrafine silica 1 copy

After mechanical foaming, it is applied by scraping method.

(f) The drying in the step adopts microwave drying, and the microwave is 10KV.

Embodiment 2 :

(a) The base fabric in the step is HS-1028, 1.0mm, 280g/ ^m2 high-density non-woven fabric from Fujian Nanfang Co., Ltd.

(b) The formulation of the treatment agent solution in the step is: polyvinyl alcohol 3 copies Fiber softener 1.5 servings water 100 copies

The liquid carrying rate of the pretreated base cloth is 50%.

(c) The drying temperature in the step is 150°C.

(d) The formula of water-based polyurethane slurry in the step is: Anionic Aromatic Waterborne Polyurethane 100 copies Polyurethane thickener 1 copy water-based paint paste 1 copy

After impregnation, the liquid-carrying rate of the non-woven fabric is 50%.

(e) The formula of water-based polyurethane slurry in the step is: Anionic Aromatic Waterborne Polyurethane 100 copies fatty acid salt surfactant 1.5 servings Succinamide salt 2 copies Polyurethane thickener 1 copy water-based paint paste 1 copy Lignocellulosic 1 copy

Apply by roller coating after mechanical foaming.

(f) The drying in the step adopts microwave drying, and the microwave is 10KV.

Embodiment 3 :

(a) The base fabric in the step is made of Fujian Nanfang 0.55mm PU leather base fabric (black gray, wet).

(b) The formulation of the treatment agent solution in the step is: Fiber softener 1 copy water 100 copies

Steps (c) and (d) do not need to be carried out, and step (e) is carried out directly.

(e) The formula of water-based polyurethane slurry in the step is: Anionic Aliphatic Waterborne Polyurethane 100 copies fatty acid salt surfactant 2 copies Succinamide salt 3 copies acrylic thickener 4 parts water-based paint paste 1 copy Isocyanate crosslinking agent 3 copies Ultrafine silica 1 copy

After mechanical foaming, it is applied by scraping method.

(f) In the step of drying, infrared heating is adopted, and the temperature gradient of the oven is 50-70-90-110-130°C.

Embodiment 4 :

(a) The base fabric in the step is made of Haining Howard Johnson warp-knitted 0.7mm black imitation cashmere.

(b) The formulation of the treatment agent solution in the step is: Fiber softener 3 copies water 100 copies

The liquid carrying rate of the pretreated base cloth is 50%.

(c) The drying temperature in the step is 150°C.

Steps (c), (d) do not need to be carried out, and step (e) is directly carried out;

(e) The formula of water-based polyurethane slurry in the step is: Anionic Aromatic Waterborne Polyurethane 100 copies fatty acid salt surfactant 1.5 servings Succinamide salt 2 copies Polyurethane thickener 1 copy water-based paint paste 1 copy Lignocellulosic 1 copy

After mechanical foaming, it is applied by scraping method.

(f) In the step of drying, infrared heating is adopted, and the temperature gradient of the oven is 50-70-90-110-130°C.

Embodiment 5 :

(a) The base fabric in the step is 50Dx75D 140g warp-knitted suede from Wujiang Wanlong Textile Co., Ltd.

(b) The formulation of the treatment agent solution in the step is: Fiber softener 1 copy water 100 copies

The liquid carrying rate of the pretreatment base cloth is 40%;

Steps (c), (d) do not need to be carried out, and step (e) is directly carried out;

(e) The formula of water-based polyurethane slurry in the step is: Anionic Aromatic Waterborne Polyurethane 100 copies fatty acid salt surfactant 1.5 servings Succinamide salt 2 copies Polyurethane thickener 1 copy water-based paint paste 1 copy Lignocellulosic 1 copy

After mechanical foaming, it is applied by scraping method.

(f) In the step of drying, infrared heating is adopted, and the temperature gradient of the oven is 50-70-90-110-130°C.

Claims (7)

1. the manufacture method of an aqueous polyurethane synthetic leather base is characterized in that: comprise the steps successively

(a) prepare base fabric:

(b) preliminary treatment: finishing agent solution formula ratio is:

Water soluble polymer: 0-3 part;

Organosilicon drilling additives: 1-3 part;

Water: 100 parts;

Preliminary treatment base fabric liquid carrying rate is 30 ~ 100%;

(e) apply the aqueous polyurethane intumescent coating: aqueous polyurethane foaming layer formula of size ratio is:

Waterborne polyurethane resin: 100 parts;

Foaming agent: 1.5-2 part;

Foam stabilizer: 2-3 part;

Thickener: 1-4 part;

Colouring agent: 1 part;

Crosslinking agent: 0-3 part;

Physique filler: 1 part;

The foaming slurry density is 300 ~ 700g/L; The every square meter coating weight of coating liquid is 100 ~ 800g/m ²

(f) Infrared Heating or microwave dryer are adopted in oven dry, oven dry usually.

2. the manufacture method of a kind of aqueous polyurethane synthetic leather base according to claim 1 is characterized in that: water soluble polymer content is 2-3 part in the described step (b), and preliminary treatment base fabric liquid carrying rate is 50 ~ 80; (e) the foaming slurry density is 400 ~ 600g/L in the step; The every square meter coating weight of coating liquid is 200 ~ 500g/m ²

3. the manufacture method of a kind of aqueous polyurethane synthetic leather base according to claim 1 and 2 is characterized in that: water soluble polymer is polyvinyl alcohol, cellulose derivative, gelatin or modified starch in the step (b); Organosilicon drilling additives is amido silicon oil or amino-modified silicone oil softener; Waterborne polyurethane resin is anion fat adoption ester type, anion fat adoption ether type, anion fat adoption ester-polyether-type, anion aromatic polyester type, anion aromatic polyether type or anion aromatic polyester-polyether-type in the step (e); Thickener is acrylic thickener, polyurethanes thickener or cellulose thickener; Crosslinking agent is isocyanate-based crosslinking agent or melamine-type crosslinking agent; Colouring agent is aqueous pigment cream or dyestuff; Foaming agent is fatty acid salt surfactant, fatty alcohol sulphuric acid salt surfactant, alkyl benzene sulphonate surfactant; Foam stabilizer is fatty acid amide surfactants, amine-oxides surfactant or cationic surfactant; The physique filler is superfine silicon dioxide, Paris white, ultra-fine natural skin powder, natural feather powder, natural wool powder, natural silk powder or lignocellulose.

4. the manufacture method of a kind of aqueous polyurethane synthetic leather base according to claim 3 is characterized in that: water soluble polymer is a polyvinyl alcohol in the step (b); Organosilicon drilling additives is the amino-modified silicone oil softener; Waterborne polyurethane resin is anion fat adoption ester-polyether-type and anion aromatic polyester-polyether-type in the step (e); Thickener is acrylic thickener, polyurethanes thickener or cellulose thickener, preferably uses acrylic compounds and polyurethanes thickener; Crosslinking agent is isocyanate-based crosslinking agent; Colouring agent is aqueous pigment cream or dyestuff, preferably uses aqueous pigment cream; Foaming agent is fatty acid salt surfactant and alkyl benzene sulphonate surfactant; Foam stabilizer is a fatty acid amide surfactants; The physique filler is superfine silicon dioxide, lignocellulose, Paris white or ultra-fine natural skin powder.

5. the manufacture method of a kind of aqueous polyurethane synthetic leather base according to claim 1 is characterized in that: described (b) step and (e) between also comprise following two steps:

(c) oven dry: bake out temperature is 80 ~ 160 ℃ ℃;

(d) steep water based polyurethane slurry: the pulp solution formula rate is as follows

Waterborne polyurethane resin: 100 parts;

Water: 0-30 part;

Thickener: 1-4 part;

Colouring agent: 1-3 part;

Crosslinking agent: 0-1 part;

Dipping back nonwoven fabric liquid carrying rate 50 ~ 60%.

6. the manufacture method of a kind of aqueous polyurethane synthetic leather base according to claim 5 is characterized in that: bake out temperature is 130 ~ 150 ℃ in described (c) step; Waterborne polyurethane resin is anion fat adoption ester type, anion fat adoption ether type, anion fat adoption ester-polyether-type, anion aromatic polyester type, anion aromatic polyether type or anion aromatic polyester-polyether-type in the step (d); Thickener is acrylic thickener, polyurethanes thickener or cellulose thickener; Crosslinking agent is isocyanate-based crosslinking agent or melamine-type crosslinking agent; Colouring agent is aqueous pigment cream or dyestuff.

7. the manufacture method of a kind of aqueous polyurethane synthetic leather base according to claim 6 is characterized in that: waterborne polyurethane resin is anion fat adoption ester-polyether-type and anion aromatic polyester-polyether-type in the described step (d); Thickener is acrylic compounds or polyurethanes thickener; Crosslinking agent is isocyanate-based crosslinking agent; Colouring agent is an aqueous pigment cream.