CN102080332A - Preparation method of waterborne polyurethane synthetic leather base - Google Patents
Preparation method of waterborne polyurethane synthetic leather base Download PDFInfo
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Abstract
The invention relates to a preparation method of a waterborne polyurethane synthetic leather base. A waterborne polyurethane resin takes water as a dispersing medium, is nontoxic, environmentally-friendly, safe and inflammable and is an optimal substitute product for a solvent resin. However, the application of the waterborne polyurethane resin to synthetic leather is relatively hysteretic, and is mainly concentrated on surface finishing of the synthetic leather. The preparation method of the waterborne polyurethane synthetic leather base comprises the following steps of: designing a base fabric; pretreating; drying; soaking in waterborne polyurethane slurry; coating a waterborne polyurethane foamed coating; and drying. The product has the basic structure of a solvent type wet process synthetic leather base and has handfeel and physical properties close to those of the solvent type synthetic leather base; solvents are not used for processing in the entire production process; the preparation method can be applied to post-processing manufacturing of any synthetic leather product; and a waterborne polyurethane material is used for post-processing, so that the synthetic leather base can be used for manufacturing shoe leather, sofa leather, case leather, clothes leather and the like.
Description
Technical field
The present invention relates to the manufacture method of a kind of aqueous polyurethane synthetic leather base.
Background technology
Contain a large amount of volatile organic solvent (VOC) in the solvent type resin, in use enter atmosphere, not only destroy environment, be detrimental to health, also cause the waste of the resource and the energy simultaneously.Present whole synthetic leather industry production processing all is to be based upon based in the basic unit of solvent borne polyurethane, in the production process in a large number with an organic solvent, as dimethyl formamide, MEK, acetone, toluene, ethyl acetate etc., these solvents are very harmful to human body.General use for synthetic leather polyurethane resin solid content is about 30%, and the organic solvent amount reaches 70%, and also can add certain amount of organic solvent again in the process of synthetic leather, so the use amount of organic solvent is bigger during actual production.Although in recent years because the rise of the prices of raw and semifnished materials, the restriction of aspects such as environment protection emission, make enterprise have to consider the recycling of solvent, the solvent recovery ability has reached about 90%, but still have the solvent about 10% to reclaim, mode with gas and waste water has been discharged in the environment, and environment and human body have been caused very big harm.
Waterborne polyurethane resin is to be decentralized medium with water, has nontoxic, environmental protection, safety, advantage such as do not fire, and be the best substitute products of solvent type resin.But the application of waterborne polyurethane resin on synthetic leather relatively lags behind comparatively speaking, mainly concentrate on the surface finish of synthetic leather, have only the water-based dry method to move technology such as membrane technology and printing and be applied in the actual production, aqueous polyurethane synthetic leather base also only is in the development in laboratory stage.
Summary of the invention
The manufacture method that the purpose of this invention is to provide a kind of aqueous polyurethane synthetic leather base, by adopting waterborne polyurethane resin can make the aqueous polyurethane use for synthetic leather semi-finished product of nonwoven fabric base with similar solvent-borne type wet-process coating, the structure of itself and solvent-borne type wet method base is similar, but production process uses the waterborne polyurethane resin of more environmental protection to make synthetic leather base.
The technical solution adopted in the present invention is: the manufacture method of a kind of aqueous polyurethane synthetic leather base is characterized in that: comprise the steps successively
(a) prepare base fabric: base fabric is selected a kind of in nonwoven fabric, woven cloth or the knitted cloth for use; 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.
Water soluble polymer content is 2-3 part in the above-mentioned steps (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
Water soluble polymer is polyvinyl alcohol, cellulose derivative, gelatin or modified starch in the above-mentioned steps (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.
Water soluble polymer is a polyvinyl alcohol in the above-mentioned steps (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.
Above-mentioned (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 aqueous polyurethane slurry is to be got by one or more mixing in waterborne polyurethane resin, thickener, crosslinking agent and the colouring agent, and its pulp solution formula rate is:
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%.
Bake out temperature is 130 ~ 150 ℃ in above-mentioned (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.
Waterborne polyurethane resin is anion fat adoption ester-polyether-type and anion aromatic polyester-polyether-type in the above-mentioned steps (d); Thickener is acrylic compounds or polyurethanes thickener; Crosslinking agent is isocyanate-based crosslinking agent; Colouring agent is an aqueous pigment cream.
The present invention has the following advantages:
Aqueous polyurethane synthetic leather base by the present invention's preparation has the basic structure of solvent-borne type wet-method synthetic leather base, and its feel and rerum natura are near solvent-borne type synthetic leather base; Do not use any solvent to process in the whole process of production; Can be used to the back processing and manufacturing of any synthetic leather product, move film, printing spraying, embossing embossing, flour milling etc., particularly select for use the back processing of waterborne polyurethane resin material to have more the feature of environmental protection as dry method; Adopt water-base polyurethane material to carry out back processing, can be used as footwear leather, sofa artificial leather, luggage leather, clothing leather etc., compare no solvent residue in finished product, health is not had harm with the solvent-borne type product; Process route of the present invention is simple, and to compare Costco Wholesale suitable with solvent-borne type, do not use solvent in the whole process of production, and basic VOC free discharging had both reduced solvent reclaimer input, use cost, had reduced energy waste and environmental pollution again.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described in detail.
Capital equipment involved in the specific embodiment of the invention comprises: put cloth holder, Chu Buji, band knobbling rolls dipping tank, be coated with conventional equipments such as head, infrared or microwave drying typing line, winder.
Employed portioned product title, purposes and behavioral illustrations in the specific embodiment of the invention:
| Material | The trade mark | Purposes | Characteristic | Producer |
| Nonwoven fabric | W-1023S120 | Base fabric | PA30/PET70，1.0mm，230g/m 2 | Fu Jiannan spins |
| Nonwoven fabric | HS-1028 | Base fabric | High density 1.0mm, 280g/m 2 | Fu Jiannan spins |
| Woven cloth | 0.55mmPU leather base cloth | Base fabric | 0.55mm polyester-cotton blend (grey black, wet) is single | Fu Jiannan spins |
| Knitted cloth | 0.7mm black is imitated cashmere | Base fabric | 0.7mm，180g?g/m 2 | Haining person of outstanding talent gives birth to through compiling |
| Knitted cloth | Through compiling suede nap | Base fabric | 50Dx75D?140?g/m 2 | The weaving of Bandung, Wujiang |
| Water soluble polymer | PVA-117 | The base fabric preliminary treatment | Polyvinyl alcohol | Japan's Kuraray |
| Organosilicon drilling additives | DH-105 | The base fabric preliminary treatment | Softening agent for fibres | The road, Yantai becomes |
| Waterborne polyurethane resin | Impranil?LP?RSC?1380 | Dipping | Anion fat family | Bayer |
| Waterborne polyurethane resin | DG-6915 | Dipping | Anion aromatic series | The road, Yantai becomes |
| Waterborne polyurethane resin | Impranil?DLU | Intumescent coating | Anion fat family | Bayer |
| Waterborne polyurethane resin | DG-6061 | Intumescent coating | Anion aromatic series | The road, Yantai becomes |
| Thickener | Borching?ALA | Dipping, intumescent coating | Acrylic compounds | Dolantin |
| Thickener | DZC-240 | Dipping, intumescent coating | Polyurethanes | The road, Yantai becomes |
| Colouring agent | ? | Dipping, intumescent coating | Aqueous color paste | Generation inscription science and technology |
| Crosslinking agent | Bayhydur?3100 | Dipping, intumescent coating | Isocyanates | Bayer |
| Foaming agent | Stockal?STA | Intumescent coating | Ammonium stearate | Germany Stockhausen |
| Foam stabilizer | Stockal?SR | Intumescent coating | The succinyl amine salt | Germany Stockhausen |
| The physique filler | OK?500 | Intumescent coating | Silica | Germany's Degussa |
| The physique filler | FD600/30 | Intumescent coating | Lignocellulose | The auspicious Mel of stepping on of Germany |
Embodiment 1:
(a) base fabric is the employing W-1023S120 of Fujian Nanfang Co., Ltd. nonwoven fabric, 1.0mm, 230g/m in the step
2, PA30/PET70;
(b) the finishing agent solution formula is in the step:
| Polyvinyl alcohol | 2 parts |
| Softening agent for fibres | 1 part |
| Water | 100 parts |
Preliminary treatment base fabric liquid carrying rate is 60%.
(c) bake out temperature is 130 ℃ in the step.
(d) the aqueous polyurethane formula of size is in the step:
| Anion fat family aqueous polyurethane | 100 parts |
| Water | 30 parts |
| Acrylic thickener | 4 parts |
| Aqueous pigment cream | 3 parts |
| The isocyanates crosslinking agent | 1 part |
Dipping back nonwoven fabric liquid carrying rate 60%.
(e) the aqueous polyurethane formula of size is in the step:
| Anion fat family aqueous polyurethane | 100 parts |
| The fatty acid salt surfactant | 2 parts |
| The succinyl amine salt | 3 parts |
| Acrylic thickener | 4 parts |
| Aqueous pigment cream | 1 part |
| The isocyanates crosslinking agent | 3 parts |
| Superfine silicon dioxide | 1 part |
Adopt the blade coating mode to apply behind the mechanical foaming.
(f) microwave drying, microwave 10KV are adopted in oven dry in the step.
Embodiment 2:
(a) base fabric is the employing HS-1028 of Fujian Nanfang Co., Ltd., 1.0mm, 280g/m in the step
2High-density non-woven fabrics.
(b) the finishing agent solution formula is in the step:
| Polyvinyl alcohol | 3 parts |
| Softening agent for fibres | 1.5 part |
| Water | 100 parts |
Preliminary treatment base fabric liquid carrying rate is 50%.
(c) bake out temperature is 150 ℃ in the step.
(d) the aqueous polyurethane formula of size is in the step:
| The anion aromatic waterborne polyurethane | 100 parts |
| The polyurethanes thickener | 1 part |
| Aqueous pigment cream | 1 part |
Dipping back nonwoven fabric liquid carrying rate 50%.
(e) the aqueous polyurethane formula of size is in the step:
| The anion aromatic waterborne polyurethane | 100 parts |
| The fatty acid salt surfactant | 1.5 part |
| The succinyl amine salt | 2 parts |
| The polyurethanes thickener | 1 part |
| Aqueous pigment cream | 1 part |
| Lignocellulose | 1 part |
Adopt roll coating model to apply behind the mechanical foaming.
(f) microwave drying, microwave 10KV are adopted in oven dry in the step.
Embodiment 3:
(a) base fabric is single for adopting Fu Jiannan to spin 0.55mm PU leather base cloth (grey black, wet) in the step.
(b) the finishing agent solution formula is in the step:
| Softening agent for fibres | 1 part |
| Water | 100 parts |
(c), (d) two steps need not carry out, and directly carry out (e) step.
(e) the aqueous polyurethane formula of size is in the step:
| Anion fat family aqueous polyurethane | 100 parts |
| The fatty acid salt surfactant | 2 parts |
| The succinyl amine salt | 3 parts |
| Acrylic thickener | 4 parts |
| Aqueous pigment cream | 1 part |
| The isocyanates crosslinking agent | 3 parts |
| Superfine silicon dioxide | 1 part |
Adopt the blade coating mode to apply behind the mechanical foaming.
(f) the Infrared Heating mode is adopted in oven dry in the step, and the oven temperature gradient is at 50-70-90-110-130 ℃.
Embodiment 4:
(a) base fabric is given birth to through compiling the imitative cashmere of 0.7mm black for adopting Haining person of outstanding talent in the step.
(b) the finishing agent solution formula is in the step:
| Softening agent for fibres | 3 parts |
| Water | 100 parts |
Preliminary treatment base fabric liquid carrying rate is 50%.
(c) bake out temperature is 150 ℃ in the step.
(c), (d) two steps need not carry out, and directly carry out (e) step;
(e) the aqueous polyurethane formula of size is in the step:
| The anion aromatic waterborne polyurethane | 100 parts |
| The fatty acid salt surfactant | 1.5 part |
| The succinyl amine salt | 2 parts |
| The polyurethanes thickener | 1 part |
| Aqueous pigment cream | 1 part |
| Lignocellulose | 1 part |
Adopt the blade coating mode to apply behind the mechanical foaming.
(f) the Infrared Heating mode is adopted in oven dry in the step, and the oven temperature gradient is at 50-70-90-110-130 ℃.
Embodiment 5:
(a) base fabric is to adopt Bandung, Wujiang 50Dx75D 140g of Fabritex S.r.l. through compiling suede nap in the step.
(b) the finishing agent solution formula is in the step:
| Softening agent for fibres | 1 part |
| Water | 100 parts |
Preliminary treatment base fabric liquid carrying rate is 40%;
(c), (d) two steps need not carry out, and directly carry out (e) step;
(e) the aqueous polyurethane formula of size is in the step:
| The anion aromatic waterborne polyurethane | 100 parts |
| The fatty acid salt surfactant | 1.5 part |
| The succinyl amine salt | 2 parts |
| The polyurethanes thickener | 1 part |
| Aqueous pigment cream | 1 part |
| Lignocellulose | 1 part |
Adopt the blade coating mode to apply behind the mechanical foaming.
(f) the Infrared Heating mode is adopted in oven dry in the step, and the oven temperature gradient is at 50-70-90-110-130 ℃.
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.
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