CN105255155A - Polyurethane composition for synthetic leather - Google Patents
Polyurethane composition for synthetic leather Download PDFInfo
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- CN105255155A CN105255155A CN201510706351.9A CN201510706351A CN105255155A CN 105255155 A CN105255155 A CN 105255155A CN 201510706351 A CN201510706351 A CN 201510706351A CN 105255155 A CN105255155 A CN 105255155A
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- polyurethane composition
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Abstract
The invention provides a polyurethane composition for synthetic leather. The pH value of the polyurethane composition is 6.0 to 7.5. Due to the fact that the pH value of the polyurethane composition is 6.0 to 7.5, the prepared synthetic leather has good acid resistance and facilitates DMF recovery.
Description
Technical field
The invention belongs to technical field of synthetic leather, being specifically related to a kind of polyurethane composition of the use for synthetic leather for applying fabricbase technique.
Background technology
Due to the reinforcement of the restriction and countries in the world that the are subject to natural condition consciousness of watching for animals; the use of natural leather reduces gradually; synthetic leather has become the best substitute of natural leather; particularly microfiber synthetic leather; because its feel, snappiness and texture are close with natural leather, and back side effect also reaches the level of natural leather.It is base cloth that existing microfiber synthetic leather have employed island, good back side effect and feel is realized by techniques such as Alkali reduction or toluene decrements, make its price considerably beyond common synthetic leather to the consumption of slurry and the treatment process process of complexity when the selection of its raw material, decrement, and Alkali reduction and toluene decrement have and large harm for processing staff's body and mind, moreover, alkali after decrement or the recovery of toluene also more difficult, correspondingly create larger environmental issue, and super fine complex process, long flow path, also create larger energy consumption problem.
The pH value of the polyurethane composition of traditional PU synthetic leather production, all between 8.0-9.4, is unfavorable for that DMF reclaims.Reach the requirement of pH value 6.0-7.5, then want double product to carry out pickling, make half-finished pH value reach 6.0-7.5.And pickling normally used be phosphoric acid, adding of phosphoric acid makes water body souring in the middle of production process, follow-uply needs to add sodium hydroxide to carry out neutralization acid, not so can affect the rate of recovery and the recovery system of DMF in the DMF aqueous solution.The reaction equation of DMF hydrolysis is as follows:
Above-mentioned reaction is reversible reaction, when reaching chemical equilibrium, positive reaction speed is equal with reversed reaction speed, the increase of any reactant concn or the minimizing of resultant, molecular balance point all will be made to move to positive reaction direction, otherwise molecular balance point will be made to move to backward reaction direction.The acidity of phosphoric acid is stronger than the acidity of formic acid (HCOOH), if phosphoric acid enters in the DMF aqueous solution, when not adding sodium hydroxide neutralization, phosphoric acid and dimethylamine react, dimethylamine concentration reduces, and impels hydrolysis to the future development of positive reaction, and the concentration of formic acid is increased.
The working concentration of usual phosphoric acid reaches 2 ~ 2.5%, wherein the phosphoric acid of 20% ~ 40% can enter into water body, phosphorus acid content in water body reaches 0.4% ~ 1%, and the concentration of dimethylamine DMF recovery tower when not introducing phosphoric acid is 0.59 ~ 1.47%, dimethylamine is secondary amine, and phosphoric acid is strong acid in three grades, dimethylamine (molecular weight 45.08) and phosphoric acid (molecular weight 97.97) react molar ratio is in theory 3:2, namely mass values is: 1:1.45, if therefore use the method that phosphoric acid makes the PH of product reduce, DMF percent hydrolysis can be made to improve about 1 times, large on the recovery impact of DMF.
Summary of the invention
PH value for the polyurethane composition solving existing use for synthetic leather is higher and be unfavorable for the problem of environmental protection, and the present invention proposes a kind of polyurethane composition of use for synthetic leather, and the pH value of this polyurethane composition is 6.0-7.5.
Technical scheme of the present invention is achieved in that
A polyurethane composition for use for synthetic leather, the pH value of described polyurethane composition is 6.0-7.5.
Further, described polyurethane composition is wet polyurethane composition.
Further, described polyurethane composition is dry method polyurethane composition.
Further, calculate by weight, described wet polyurethane composition comprises following component: solvent type polyurethane resin 50-80 part, lignocellulose 10-20 part, pH adjusting agent 10-40 part and dimethyl formamide 80-100 part.
Further, the molecular weight of described solvent type polyurethane resin is 100,000-60 ten thousand; One or more in described pH adjusting agent calcium phosphate, aluminium hydroxide and calcium sulfate.
Further, calculate by weight, described dry method polyurethane composition comprises following component: solvent type polyurethane resin 80-100 part, acid additive 1-2 part, dimethyl formamide 5-30 part and ethyl acetate 10-20 part.
Further, the molecular weight of described solvent type polyurethane resin is 100,000-40 ten thousand; Described acid additive is acetic acid and/or citric acid.
The method of wet polyurethane composition production synthetic leather is as follows:
Calculate by weight, take solvent type polyurethane resin 50-80 part, lignocellulose 10-20 part, pH adjusting agent 10-40 part and dimethyl formamide 80-100 part, join in batching kettle and stir, batching is coated on the base cloth after washing and be dry, enters coagulating pan (20 ~ 31%DMF aqueous solution of mass percent) and solidify, through washing and oven dry after solidifying, produce synthetic leather work in-process.
The method that dry method polyurethane composition produces synthetic leather is as follows:
Calculate by weight, take solvent type polyurethane resin 80-100 part, acid additive 1-2 part, dimethyl formamide 5-30 part and ethyl acetate 10-20 part, join in batching kettle and stir, be coated in separate-type paper after stirring, the first layer coating is surface layer, second layer coating is adhesive linkage, fit at laminating wheel, more residual organic solvent is dried, then through overcooling after bonding, finished product is peeled off from separate-type paper, forms final product.
Beneficial effect of the present invention:
1, the maximum reason that the pH value of the polyurethane composition of general use for synthetic leather is high is calcium carbonate, and 2 grams of calcium carbonate are dissolved in 100 ml waters, and PH reaches more than 9.4.In the recipe determination process of wet polyurethane composition, by selecting one or more pH adjusting agents in aluminium hydroxide, calcium phosphate and calcium sulfate as filler, after this several stopping composition replaces calcium carbonate completely, between the pH value 7.5 ~ 7.6 of synthetic leather.Continuation needs between will reaching 6.0 ~ 7.0 to carry out acid adding adjustment to dry method formula, through experimental data after synthetic leather dry method slurry adds the acetic acid of 1 ~ 2%, in conjunction with the synthetic leather work in-process of pH value 7.5 ~ 7.6, the product P H value produced is between 6.2 ~ 7.0.
2, the synthetic leather using the polyurethane composition of use for synthetic leather of the present invention to prepare, its pH value reaches 6.0 ~ 7.5, have the following advantages: 1) pH value of the normal skin of people is in 5.0 ~ 7.0 these scopes, and synthetic leather is more than more than 7.5, some skin can not feel well than more sensitive crowd, and the synthetic leather prepared with polyurethane composition of the present invention can improve the comfort level of people; 2) be exactly synthetic leather when slant acidity pH value 5.0 ~ 7.0, hydrolysis rate is starkly lower than the synthetic leather of meta-alkalescence (pH value 8 ~ 10), uses synthetic leather long service life prepared by polyurethane composition of the present invention.
Embodiment
Embodiment 1
The formula of wet polyurethane composition:
Solvent type polyurethane resin 80 parts, lignocellulose 10 parts, 10 parts, calcium phosphate, 10 parts, aluminium hydroxide and dimethyl formamide 80 parts, wherein urethane resin molecular weight is 100,000.
Wet polyurethane composition production synthetic leather:
Above-mentioned batching is joined in batching kettle and stirs, batching is coated on the base cloth after washing and be dry, enter coagulating pan (the 20%DMF aqueous solution of mass percent) to solidify, through washing and oven dry after solidifying, produce synthetic leather work in-process.
Embodiment 2
The formula of wet polyurethane composition:
Solvent type polyurethane resin 50 parts, lignocellulose 20 parts, 20 parts, aluminium hydroxide, calcium sulfate part 20 parts and dimethyl formamide 80-100 part, wherein urethane resin molecular weight is 400,000.
Wet polyurethane composition production synthetic leather:
Above-mentioned batching is joined in batching kettle and stirs, batching is coated on the base cloth after washing and be dry, enter coagulating pan (the 31%DMF aqueous solution of mass percent) to solidify, through washing and oven dry after solidifying, produce synthetic leather work in-process.
Embodiment 3
The formula of dry method polyurethane composition:
Solvent type polyurethane resin 80 parts, citric acid 1 part, dimethyl formamide 30 parts and ethyl acetate 10 parts, wherein urethane resin molecular weight is 600,000.
The method that dry method polyurethane composition produces synthetic leather is as follows:
Above-mentioned batching is joined in batching kettle and stirs, be coated on after stirring in separate-type paper, the first layer coating is surface layer, second layer coating is adhesive linkage, fit at laminating wheel, more residual organic solvent is dried, then through overcooling after bonding, finished product is peeled off from separate-type paper, forms final product.
Embodiment 4
The formula of dry method polyurethane composition:
Solvent type polyurethane resin 100 parts, acetic acid 2 parts, dimethyl formamide 5 parts and ethyl acetate 20 parts, wherein urethane resin molecular weight is 100,000.
The method that dry method polyurethane composition produces synthetic leather is as follows:
Above-mentioned batching is joined in batching kettle and stirs, be coated on after stirring in separate-type paper, the first layer coating is surface layer, second layer coating is adhesive linkage, fit at laminating wheel, more residual organic solvent is dried, then through overcooling after bonding, finished product is peeled off from separate-type paper, forms final product.
Embodiment 5
Synthetic leather prepared by embodiment 4 is entered ageing-resistant experiment, the results are shown in Table 1:
The ageing-resistant experiment of table 1 synthetic leather
As can be seen from Table 1, synthetic leather anti-hydrolytic performance is in acid condition than good under alkaline condition.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a polyurethane composition for use for synthetic leather, is characterized in that, the pH value of described polyurethane composition is 6.0-7.5.
2. the polyurethane composition of use for synthetic leather according to claim 1, is characterized in that, described polyurethane composition is wet polyurethane composition.
3. the polyurethane composition of use for synthetic leather according to claim 1, is characterized in that, described polyurethane composition is dry method polyurethane composition.
4. the polyurethane composition of use for synthetic leather according to claim 2, it is characterized in that, calculate by weight, described wet polyurethane composition comprises following component: solvent type polyurethane resin 50-80 part, lignocellulose 10-20 part, pH adjusting agent 10-40 part and dimethyl formamide 80-100 part.
5. the polyurethane composition of use for synthetic leather according to claim 4, is characterized in that, the molecular weight of described solvent type polyurethane resin is 100,000-60 ten thousand; One or more in described pH adjusting agent calcium phosphate, aluminium hydroxide and calcium sulfate.
6. the polyurethane composition of use for synthetic leather according to claim 3, it is characterized in that, calculate by weight, described dry method polyurethane composition comprises following component: solvent type polyurethane resin 80-100 part, acid additive 1-2 part, dimethyl formamide 5-30 part and ethyl acetate 10-20 part.
7. the polyurethane composition of use for synthetic leather according to claim 6, is characterized in that, the molecular weight of described solvent type polyurethane resin is 100,000-40 ten thousand; Described acid additive is acetic acid and/or citric acid.
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| CN201510706351.9A CN105255155B (en) | 2015-10-26 | 2015-10-26 | The urethane composition of use for synthetic leather |
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| CN201510706351.9A CN105255155B (en) | 2015-10-26 | 2015-10-26 | The urethane composition of use for synthetic leather |
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| CN105255155A true CN105255155A (en) | 2016-01-20 |
| CN105255155B CN105255155B (en) | 2018-02-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108841163A (en) * | 2018-07-06 | 2018-11-20 | 山东圣泉新材料股份有限公司 | Modified polyurethane resin and preparation method thereof, modified polyurethane artificial leather and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1160936A (en) * | 1997-08-28 | 1999-03-05 | Dainippon Ink & Chem Inc | Crosslinkable polyurethane resin composition and artificial leather and synthetic leather using the same |
| CN101994263A (en) * | 2009-08-20 | 2011-03-30 | 日华化学株式会社 | Method for producing leather material and leather material |
| JP2013189736A (en) * | 2012-02-14 | 2013-09-26 | Toyo Cloth Co Ltd | Synthetic leather |
| CN103498344A (en) * | 2013-10-17 | 2014-01-08 | 安徽安利合成革股份有限公司 | Production method of nano composite green flame-retardant polyurethane synthetic leather |
| CN104695236A (en) * | 2015-04-01 | 2015-06-10 | 华大化学集团有限公司 | Method for producing water-based polyurethane synthetic leather |
-
2015
- 2015-10-26 CN CN201510706351.9A patent/CN105255155B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1160936A (en) * | 1997-08-28 | 1999-03-05 | Dainippon Ink & Chem Inc | Crosslinkable polyurethane resin composition and artificial leather and synthetic leather using the same |
| CN101994263A (en) * | 2009-08-20 | 2011-03-30 | 日华化学株式会社 | Method for producing leather material and leather material |
| JP2013189736A (en) * | 2012-02-14 | 2013-09-26 | Toyo Cloth Co Ltd | Synthetic leather |
| CN103498344A (en) * | 2013-10-17 | 2014-01-08 | 安徽安利合成革股份有限公司 | Production method of nano composite green flame-retardant polyurethane synthetic leather |
| CN104695236A (en) * | 2015-04-01 | 2015-06-10 | 华大化学集团有限公司 | Method for producing water-based polyurethane synthetic leather |
Non-Patent Citations (1)
| Title |
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| 徐培林: "《聚氨酯材料手册》", 31 August 2002, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108841163A (en) * | 2018-07-06 | 2018-11-20 | 山东圣泉新材料股份有限公司 | Modified polyurethane resin and preparation method thereof, modified polyurethane artificial leather and application |
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