CN105255155B - The urethane composition of use for synthetic leather - Google Patents
The urethane composition of use for synthetic leather Download PDFInfo
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- CN105255155B CN105255155B CN201510706351.9A CN201510706351A CN105255155B CN 105255155 B CN105255155 B CN 105255155B CN 201510706351 A CN201510706351 A CN 201510706351A CN 105255155 B CN105255155 B CN 105255155B
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Abstract
The present invention proposes a kind of urethane composition of use for synthetic leather, and the pH value of the urethane composition is 6.0 7.5.The pH value of the urethane composition is 6.0 7.5, and the synthetic leather acid resistance being prepared is good, and is advantageous to DMF recovery.
Description
Technical field
The invention belongs to technical field of synthetic leather, and in particular to a kind of poly- ammonia of use for synthetic leather for coated cloth base technique
Ester composition.
Background technology
Because what the restriction by natural conditions and countries in the world protection animal were realized strengthens, the use of natural leather is
Gradually decrease, synthetic leather is into the best substitute of natural leather, particularly microfiber synthetic leather, because of its feel, pliability and matter
Sense is close with natural leather, and back side effect has also reached the level of natural leather.Existing microfiber synthetic leather employs island
For base fabric, good back side effect and feel, the selection of its raw material, decrement are realized by the technique such as Alkali reduction or toluene decrement
When consumption to slurry and the handling process process of complexity make its price considerably beyond common synthetic leather, and Alkali reduction and first
Benzene decrement has for processing staff's body and mind and big harm, and moreover, the recovery of alkali or toluene after being reduced also is compared
Difficulty, larger environmental issue, and the complex process of woven fabric, long flow path are accordingly generated, also generates larger energy consumption problem.
The pH value of the urethane composition of traditional PU synthetic leather productions is unfavorable for DMF and returned all between 8.0-9.4
Receive.Reach pH value 6.0-7.5 requirement, then want double of product to carry out pickling, the pH value of semi-finished product is reached 6.0-7.5.And
Pickling it is usually used be phosphoric acid, the addition of phosphoric acid makes water body souring among production process, subsequently need add sodium hydroxide enter
Row neutralizes acidity, not so can influence the rate of recovery and reclaimer of DMF in the DMF aqueous solution.The reaction equation of DMF hydrolysis is such as
Under：
Above-mentioned reaction is reversible reaction, and when reaching chemical balance, positive reaction speed is equal with back reaction speed, any anti-
The increase of thing concentration or the reduction of product are answered, reaction equalization point will all moved to positive reaction direction, otherwise reaction will be made
Equalization point moves to backward reaction direction.The acidity of phosphoric acid is stronger than the acidity of formic acid (HCOOH), if phosphoric acid enters DMF water
In solution, be added without in the case that sodium hydroxide neutralizes, phosphoric acid and dimethylamine are reacted, and dimethylamine concentration is reduced, promote hydrolysis to
The direction of positive reaction is developed, and increases the concentration of formic acid.
The concentration of usual phosphoric acid reaches 2~2.5%, wherein 20%~40% phosphoric acid can enter water body, water body
In phosphorus acid content reach 0.4%~1%, and dimethylamine concentration of DMF recovery towers in the case of no introducing phosphoric acid exists
0.59~1.47%, dimethylamine is secondary amine, and phosphoric acid is strong acid in three-level, in theory dimethylamine (molecular weight 45.08) and phosphorus
Sour (molecular weight 97.97) reaction molar ratio is 3:2, i.e. mass values are：1:1.45, so if making product using phosphoric acid
The method that PH is reduced, DMF percent hydrolysis can be made to improve 1 times or so, the recovery on DMF influences big.
The content of the invention
To solve the problems, such as that the pH value of the urethane composition of existing use for synthetic leather is higher and is unfavorable for environmental protection, the present invention
A kind of urethane composition of use for synthetic leather is proposed, the pH value of the urethane composition is 6.0-7.5.
The technical proposal of the invention is realized in this way：
A kind of urethane composition of use for synthetic leather, the pH value of the urethane composition is 6.0-7.5.
Further, the urethane composition is wet polyurethane composition.
Further, the urethane composition is dry method urethane composition.
Further, in parts by weight, the wet polyurethane composition includes following components：Solvent borne polyurethane tree
Fat 50-80 parts, lignocellulosic 10-20 parts, pH adjusting agent 10-40 parts and dimethylformamide 80-100 parts.
Further, the molecular weight of the solvent type polyurethane resin is 100,000-60 ten thousand；The pH adjusting agent calcium phosphate, hydrogen
Aluminum oxide and the one or more in calcium sulfate.
Further, in parts by weight, the dry method urethane composition includes following components：Solvent borne polyurethane tree
Fat 80-100 parts, acid additive 1-2 parts, dimethylformamide 5-30 parts and ethyl acetate 10-20 parts.
Further, the molecular weight of the solvent type polyurethane resin is 100,000-40 ten thousand；The acid additive be acetic acid and/
Or citric acid.
The method of wet polyurethane composition production synthetic leather is as follows：
In parts by weight, solvent type polyurethane resin 50-80 parts, lignocellulosic 10-20 parts, pH adjusting agent are weighed
10-40 parts and dimethylformamide 80-100 parts, are added in batching kettle and are stirred, and dispensing is coated in by washing and scalded
In base fabric after dry, solidified into coagulating basin (20~31%DMF aqueous solution of mass percent), by washing after solidification
And drying, produce synthetic leather semi-finished product.
The method of dry method urethane composition production synthetic leather is as follows：
In parts by weight, solvent type polyurethane resin 80-100 parts, acid additive 1-2 parts, dimethyl formyl are weighed
Amine 5-30 parts and ethyl acetate 10-20 parts, are added in batching kettle and are stirred, be coated on after stirring in release liners, the
One layer of coating is surface layer, and second layer coating is adhesive linkage, is bonded in laminating wheel, the organic solvent of residual is entered again after bonding
Row drying, then through supercooling, finished product is peeled off from release liners, forms final product.
Beneficial effects of the present invention：
1st, the high maximum reason of the pH value of the urethane composition of general use for synthetic leather is calcium carbonate, and 2 grams of calcium carbonate are molten
In 100 milliliters of water, PH reaches more than 9.4.During the recipe determination of wet polyurethane composition, by from hydroxide
One or more pH adjusting agents in aluminium, calcium phosphate and calcium sulfate are as filler, after this several inserts substitutes calcium carbonate completely,
Between the pH value 7.5~7.6 of synthetic leather.Continue to need to carry out acid adding adjustment to dry method formula between reaching 6.0~7.0, pass through
Experimental data is after the acetic acid of synthetic leather dry method slurry addition 1~2%, with reference to the synthetic leather semi-finished product of pH value 7.5~7.6, institute
The product pH value produced is between 6.2~7.0.
2nd, the synthetic leather being prepared using the urethane composition of use for synthetic leather of the present invention, its pH value reaches 6.0~
7.5, there is advantages below：1) pH value of the normal skin of people is in 5.0~7.0 this scope, and synthetic leather is more than more than 7.5,
Some skins can not feel well than more sensitive crowd, and the synthetic leather prepared with the urethane composition of the present invention can improve people
Comfort level；2) be exactly synthetic leather in the case of slant acidity pH value 5.0~7.0, hydrolysis rate is significantly lower than meta-alkalescence (pH value 8
~10) synthetic leather, the synthetic leather service life prepared using the urethane composition of the present invention are grown.
Embodiment
Embodiment 1
The formula of wet polyurethane composition：
80 parts of solvent type polyurethane resin, 10 parts of lignocellulosic, 10 parts of calcium phosphate, 10 parts of aluminium hydroxide and dimethyl methyl
80 parts of acid amides, wherein polyurethane resin molecular weight are 100,000.
Wet polyurethane composition production synthetic leather：
Above-mentioned dispensing is added in batching kettle and is stirred, dispensing is coated in the base fabric after washing and be dry
On, solidified into coagulating basin (the 20%DMF aqueous solution of mass percent), by washing and drying after solidification, produced
Synthetic leather semi-finished product.
Embodiment 2
The formula of wet polyurethane composition：
50 parts of solvent type polyurethane resin, 20 parts of lignocellulosic, 20 parts of aluminium hydroxide, 20 parts of calcium sulfate part and dimethyl
Formamide 80-100 parts, wherein polyurethane resin molecular weight are 400,000.
Wet polyurethane composition production synthetic leather：
Above-mentioned dispensing is added in batching kettle and is stirred, dispensing is coated in the base fabric after washing and be dry
On, solidified into coagulating basin (the 31%DMF aqueous solution of mass percent), by washing and drying after solidification, produced
Synthetic leather semi-finished product.
Embodiment 3
The formula of dry method urethane composition：
10 parts of 80 parts of solvent type polyurethane resin, 1 part of citric acid, 30 parts of dimethylformamide and ethyl acetate, wherein poly-
Urethane molecular resin amount is 600,000.
The method of dry method urethane composition production synthetic leather is as follows：
Above-mentioned dispensing is added in batching kettle and is stirred, is coated on after stirring in release liners, first layer coating
For surface layer, second layer coating is adhesive linkage, is bonded in laminating wheel, the organic solvent of residual is dried again after bonding,
Then through supercooling, finished product is peeled off from release liners, forms final product.
Embodiment 4
The formula of dry method urethane composition：
20 parts of 100 parts of solvent type polyurethane resin, 2 parts of acetic acid, 5 parts of dimethylformamide and ethyl acetate, wherein poly- ammonia
Ester molecular resin amount is 100,000.
The method of dry method urethane composition production synthetic leather is as follows：
Above-mentioned dispensing is added in batching kettle and is stirred, is coated on after stirring in release liners, first layer coating
For surface layer, second layer coating is adhesive linkage, is bonded in laminating wheel, the organic solvent of residual is dried again after bonding,
Then through supercooling, finished product is peeled off from release liners, forms final product.
Embodiment 5
Synthetic leather prepared by embodiment 4 enters ageing-resistant experiment, the results are shown in Table 1：
The ageing-resistant experiment of the synthetic leather of table 1
From table 1 it follows that the anti-hydrolytic performance of synthetic leather in acid condition is better than under alkalescence condition.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (1)
1. a kind of urethane composition of use for synthetic leather, it is characterised in that the pH value of the urethane composition is 6.0-7.5；
The urethane composition is dry method urethane composition；In parts by weight, the dry method urethane composition include with
Lower component：Solvent type polyurethane resin 80-100 parts, acid additive 1-2 parts, dimethylformamide 5-30 parts and ethyl acetate 10-
20 parts；The molecular weight of the solvent type polyurethane resin is 100,000-40 ten thousand；The 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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| CN105255155B true CN105255155B (en) | 2018-02-06 |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101994263A (en) * | 2009-08-20 | 2011-03-30 | 日华化学株式会社 | Method for producing leather material and leather material |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3867361B2 (en) * | 1997-08-28 | 2007-01-10 | 大日本インキ化学工業株式会社 | Artificial leather or synthetic leather |
| JP5992246B2 (en) * | 2012-02-14 | 2016-09-14 | 東洋クロス株式会社 | Synthetic leather |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101994263A (en) * | 2009-08-20 | 2011-03-30 | 日华化学株式会社 | Method for producing leather material and leather material |
| 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 |
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