CN1107171A - Acetate butyl fibre-propenoic acid composite leather coating and decorating material - Google Patents
Acetate butyl fibre-propenoic acid composite leather coating and decorating material Download PDFInfo
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- CN1107171A CN1107171A CN 94111930 CN94111930A CN1107171A CN 1107171 A CN1107171 A CN 1107171A CN 94111930 CN94111930 CN 94111930 CN 94111930 A CN94111930 A CN 94111930A CN 1107171 A CN1107171 A CN 1107171A
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Abstract
The present invention provides a kind of solvent type or aqueous emulsion type leather coating and decorating material using compound of multi-component copolymer of cellulose acetate butyrate and propenoic acid as film forming main builder. Between the molecula of the cellulose acetate butyrate and the molecula of propenoic acid, the fatty polyisocyanate is used to crosslink and it makes the carboxy group introduced from the macromolecular chain of the crosslinking compound react with organic poly amine compound and/or alcohol amine compound to join the polar lateral chain containing poly amine and/or carboxy group.
Description
What the present invention relates to is a kind of coating and decorating material that white leather or light-colored leather production process are made the top layer coating that is used for.
As the coating and decorating material on leather top layer, require it to become to film and lower floor between have firm tackiness, and good snappiness, elasticity, physical strength and heat-resisting winter hardiness are arranged.Also require it to have certain rigidity, anti-colliding with, anti-stroke of anti-scrape along has certain water-fast anti-organic solvent properties and comfortable corium feel, and these performances in use can keep more enduringly.For the covering with paint of white leather and light-colored leather, except that above-mentioned performance, go back the ultraviolet resistance of lay special stress on coating and decorating material, require coating inhibited from yellowing aging under long-term illumination condition.Mainly use film forming materials such as nitrocotton, urethane, casein food grade and acrylic resin in coating and decorating material field, leather top layer at present.Wherein nitrocotton cooperate with softening agent or with make leather top layer coating and decorating material after soft resin cooperates and can obtain better comprehensive performance.But the nitrocotton coating is ultraviolet resistance not, uses easy efflorescence flavescence down through long period illumination, can not be used for white leather.Casein food grade is as a kind of native protein material, cover with paint, lacquer, colour wash, etc. the back good hand touch, but its film-forming properties is poor, and is not water-fast, normally mixes use with other film forming materials such as acrylic resin.Because the casein food grade light fugitive has also limited its application on white leather.Urethane is the leather finish field of just introducing more maturely in the last few years, it is filmed and has good physical and mechanical properties and feel, but owing to be subjected to raw-material restriction, polyurethane decorative paint for leather nearly all is the aromatic urethane type at present, easily flavescence can not be used for the covering with paint of white leather under illumination condition.The acrylic resin of relatively large use has fabulous ultraviolet-resistant performance in leather finish, and ageing resistance is good, also has good physical and mechanical properties and chemical-resistant resistance and stain resistance, and these performances are very necessary for the covering with paint of white leather.Scope is narrower but acrylic resin has use temperature, use than the appropriate resin easy embrittlement in winter of filming in summer, and filming of being suitable in the winter time runs into so-called " hot sticky cold crisp " shortcoming that just can be clamminess when temperature raises, and the coated plastics sense is too strong, usually cover with paint, lacquer, colour wash, etc. more in the bottom and the middle level that are used for leather, is unsuitable for doing separately the top layer and covers with paint, lacquer, colour wash, etc.
In other application of paints fields, there is the situation of employing with cellulose acetate butyrate and acrylic resin blend use for example high-grade automotive lacquer and high-grade light furniture varnish aspect.In these application scenarios, two kinds of components of Mierocrystalline cellulose and resin only are simple mechanically mixing, and its permanent intermiscibility reaches choice of Solvent is subjected to bigger restriction, and the comprehensive characteristics of two kinds of components can not demonstrate fully.And these occasions are all used with the form of solvent-borne type product, are difficult to be prepared into the stable aqueous emulsion type product that is suitable for.In the coating material for leather field, cellulose acetate butyrate that Chinese patent 92111958.5 introduced and " nuclear-shell " composite emulsion type coating material for leather of acrylic resin are also arranged, this invention adopts the technological line of free-radical emulsion polymerization to prepare the coated material, can obtain excellent physical and mechanical properties and other good film performances, be suitable for doing the top layer coating and decorating material of white leather.But because this invention material is the particle structure of resin shell parcel Mierocrystalline cellulose nuclear, cellulose acetate butyrate is wrapped up by acrylic resin fully, and therefore, the peculiar plastic sense of its acrylic resin of filming still can not overcome preferably.
Purpose of the present invention just is to utilize to be had good physical mechanical property and comfortable feel and fast light not xanthochromia performance and occupies the cellulose acetate butyrate of coating first of Mierocrystalline cellulose and will have the acrylic resin of numerous good characteristics composite modified, to overcome the strong shortcoming of its hot sticky cold crisp and plastic sense, make it to become good white leather top layer coating and decorating material.
The object of the present invention is achieved like this:
Carried out crosslinked with polyisocyanates between the macromolecular chain of cellulose acetate butyrate and acrylic-multipolymer, and the reaction of part carboxyl on the multiple copolymer molecular chain and organic polyamine and/or alcamine compound generates amido linkage and has introduced the polar side chain that contains polyamines and/or hydroxyl.Wherein the weight ratio of cellulose acetate butyrate and acrylic-multipolymer is 0.05～1.5, the ratio of the mole number of hydroxyl is 0.1～1 in polyisocyanate-based mole number and the main film forming component, the mole dosage of organic polyamine and/or alcohol amine compound be in the main film-forming components carboxyl mole number 5～50%.
Below material of the present invention is described in further detail.
Cellulose acetate butyrate has good physical and mechanical properties and comfort feel, and particularly its fast light not xanthochromia is good.But it films harder, and to the choice of Solvent narrow range, chemical resistance is not so good, can not be used alone as coating material for leather.Yet itself and soft acrylic-multipolymer resin-bonded are got up, can learn from other's strong points to offset one's weaknesses, obtain the leather top layer coating and decorating material of high comprehensive performance.In the molecular structure of cellulose acetate butyrate, contain the secondary hydroxyl that ethanoyl, butyryl radicals and partial hydrolysis generate, can be divided into the product of plurality of specifications according to the difference of butyryl radicals content in its molecule.Though the present invention all can use at 14～47% all size product butyryl radicals content, from the particular requirement of leather finish, preferably select for use snappiness and water resisting property preferably butyryl radicals content at 34～47% cellulose acetate butyrate.The weight ratio of cellulose acetate butyrate and acrylic-multipolymer is 0.05～1.5 in the present invention, is preferably 0.1～1.If be lower than this scope, then the hot sticky cold crisp phenomenon of acrylic resin can not overcome preferably, and the acrylic resin plastic sense of filming can not be eliminated.If be higher than this scope, the tensile strength of then filming, snappiness and chemical proof, antifouling property can reduce too much.
Acrylic-multipolymer as one of main film-forming components, its main raw material is (methyl) acrylic acid derivative and vinyl monomer, as (methyl) acrylic acid methyl esters, ethyl ester, propyl ester, isopropyl ester, positive butyl ester, isobutyl ester, the tert-butyl ester, just own ester, n-octyl, 2-ethylhexyl and cyclohexyl etc., (methyl) acrylamide, propenal, allyl amine, vinylbenzene, vinyl-acetic ester, vinyl-n-butyl ether, allyl group phenylate etc.Usually select for use a kind of or several and hydroxyl monomer and contain carboxylic monomer and be used.
As the necessary component of acrylic-multipolymer among the present invention, use the hydroxyl monomer that is not less than monomer total amount 0.5%, with on the multiple copolymer molecular chain, introduce necessary can with the hydroxyl cross-linking set of isocyanic ester radical reaction.Usually can select (methyl) acrylic acid hydroxyalkyl derivant for use, as (methyl) senecioate-hydroxyl ethyl ester, (methyl) senecioate-hydroxypropyl acrylate and N hydroxymethyl acrylamide, propenyl alcohol etc.If introduce the monomer contain epoxy group(ing) as (methyl) glycidyl acrylate etc., also can play and hydroxyl monomer effect same.The monomeric consumption of this class hydroxyl (or epoxy group(ing)) is 0.5～10% of a monomer total amount, is preferably 1～8%.If be lower than this scope, then the degree of crosslinking between multiple copolymer and the cellulose acetate butyrate is low excessively, can not reach cross-linking modified effect.If be higher than this scope, then the multiple spot crosslinking degree of Xing Chenging is excessive, and the product soltion viscosity is increased greatly, and levelling property is covered with paint, lacquer, colour wash, etc. in influence, even causes the undissolved gel piece of generation in the reaction process.
Necessary component as acrylic-multipolymer, use the carboxylic monomer that contains that is not less than monomer total amount 0.5%, some generates amido linkage with organic polyamine that adds and/or alcohol amine compound reaction to the carboxyl of these introducings in final cross-linked composite, has introduced polyamines and/or hydroxyl polar side chain group on the mixture macromole.These side-chain radicals and unreacted remaining carboxyl have been given the affinity of cross-linked composite to water, increased its water miscible liquid stability, and when covering with paint, lacquer, colour wash, etc. film forming, increase and film, and it is crosslinked to react to each other in film process, has increased the mechanical property of filming the clinging power of bottom.The present invention can select for use vinylformic acid, methacrylic acid, maleic acid (acid anhydride), FUMARIC ACID TECH GRADE (acid anhydride), suitable 2-butylene acid etc. to contain carboxylic monomer, and its consumption is 0.5～8% of a monomer total amount, is preferably 1～5%.If be lower than this scope, then when material was made the use of water miscible liquid form, its stability of emulsion was relatively poor.If be higher than this scope,, can obviously reduce the water resisting property of filming then owing to wetting ability carboxyl remaining in filming is too much.
What pay special attention to is, because material of the present invention is mainly used in the top layer of white leather and covers with paint, lacquer, colour wash, etc., to the fast light not xanthochromia requirement height of filming, therefore, vinyl cyanide, divinyl and the chloroprene of using always in acrylic resin modified usually, isoprene etc. can not be selected for use the unsettled monomer of UV-light.
The polyisocyanate crosslinker that the present invention adopts is vulcabond normally.Because the reaction of isocyanate group and primary hydroxyl and secondary hydroxyl is than faster with the reaction of carboxyl and amide group, therefore under reaction conditions, two active isocyanate group on the diisocyanate molecules main with the acrylic-multipolymer molecular chain on primary hydroxyl and the reaction of the secondary hydroxyl on cellulose acetate butyrate molecule generation amino-formate bond, form cross-bridge, two or more cellulosic molecules and multiple copolymer molecule are coupled together form a bigger mixture macromole.From purposes of the present invention, can not use the aromatic diisocyanate of ultraviolet-resistant performance difference, and must use to ultraviolet light stabilized aliphatic diisocyanate inhibited from yellowing, as di-isocyanate, xylylene diisocyanate, isophorone diisocyanate, toluene cyclohexyl diisocyanate, trimethylammonium di-isocyanate, dicyclohexyl methane diisocyanate and tetramethyl-vulcabond etc.Its consumption be the isocyanate group mole number with main film-forming components in the ratio of hydroxyl mole number 0.1～1, be preferably 0.3～0.8.If be lower than this scope, then because crosslinking degree is low excessively, be difficult to the effect that reaches cross-linking modified, if exceed this scope, then the excess isocyanate base will with the carbamate radical reaction of carboxyl, amide group even formation on the multiple copolymer molecular chain, cause the multiple spot crosslinking degree excessive, make the excessive influence of the product viscosity levelling property of filming, even produce insoluble gel piece.
The present invention adopts that carboxyl reacts the generation amido linkage on organic polyamine compound and/or alcohol amine compound and the cross-linked composite macromolecular chain, introduces the polar side chain group that contains polyamines and/or hydroxyl on the mixture macromolecular chain.The side-chain radical of these introducings gives the mixture macromole certain hydrophilic ability, can strengthen the stability of its water miscible liquid.In covering with paint, lacquer, colour wash, etc. film process, these side-chain radicals again can with other groups such as cross-linking reactions such as carboxyl, amide group, the mechanical property that enhancing became to film, organic polyamine of Shi Yonging and hydramine can be selected Diethylenetriaminee (DETA), triethylenediamine, triethylenetetramine, tetraethylenepentamine, quadrol, propylene diamine, hexanediamine, Monoethanolamine MEA BASF, diethanolamine, trolamine etc. for use in the present invention, its consumption is decided on carboxyl-content in the cross-linked composite, usually the ratio of carboxyl mole number is 0.05～0.6 in its mole number and the main film-forming components, is preferably 0.1～0.5.If be lower than this scope, the then less stable when material preparation of the present invention becomes water miscible liquid.If exceed this scope, then, be directed at the water repelling property of filming and reduce significantly owing to uncrosslinked hydrophilic side chain base remaining after the covering with paint film forming is too much.
Except that main film-forming components, also can add some other subsidiary material, to give some specific function of filming.As having smooth hand feeling, add the silicone oil of filmogen gross weight 0.1～5% in order to make to film.In order to reduce coating film gloss adds filmogen gross weight 1～10% with outstanding pure white effect wax (synthetic macromolecule wax or mineral wax or animal wax).The adding of wax also can be given the careful sense of more comfortable wax of filming.Can add static inhibitor in addition and stain, add uvioresistant photo etching and oxidation inhibitor with the further raising fast light ageing resistance etc. of filming with the attached dirt that reduces coating.Usually these interpolation material gross weights are no more than 5% of film-forming components.When adding good Rutile type Titanium Dioxide or the fast light white pigment cream of photostabilization, and make face/base in the system at 20～55% o'clock, then can obtain pure whiter filming than being.
The present invention is cross-linked into new mixture macromole with cellulose acetate butyrate and acrylic-multipolymer, the cellulose acetate butyrate restriction too narrow to the solvent range of choice when having improved the intermiscibility of two kinds of components and having broken through simple blend makes usually used acetates, ketone, alcohols, pure ethers and petroleum aromatics kind solvent all can select for use.Generally be to select for use two or more solvent to be used.Be noted that before not finishing the crosslinking reaction of main film-forming components, the solvent that can not use alcohols, alcohol ether etc. to react with vulcabond, this kind solvent can only use in the later stage.
When material preparation of the present invention becomes aqueous emulsion type to use, use emulsifying agent.Normally used various non-ionic type, cationic and anionic emulsifier all can be selected for use.Emulsifying agent can use merely, but generally is that 2 to 3 kinds of emulsifying agents are used, to obtain better emulsifying effectiveness.Contain the polyamines polar chain based on having introduced in the material of the present invention, common positively charged situation is not generally used electronegative anionic emulsifier merely, but anionic emulsifier and nonionic emulsifying agent is used under low pH value condition.For further improving stability of emulsion, also can add the assistant for emulsifying agent that is no more than emulsion amount 3%, as pure ethers, long-chain fat alcohols etc.
Because moisture content easily generates urea with the polyisocyanates reaction, has not only consumed linking agent, its formula rate is changed, and the urea that produces also may be further crosslinked with polyisocyanates reaction formation multiple spot, causes the gelation of product.Therefore in material preparation process of the present invention, before the multi isocyanate crosslinking reaction, should be specifically noted that and avoid bringing into of moisture content.Production unit and container should be dry, and water content should be less than 0.5% in used starting material monomer and the solvent.If necessary, can be at multiple copolymer feed inert nitrogen or make to be reflected under the solvent refluxing state in the synthetic and crosslinking reaction process and carry out, with the interference of the oxygen in the excluding air and moisture content reaction.
The difference of the present invention and currently available products technology is to have adopted the polyisocyanates of the tool fat chain structure of ultraviolet light stabilized coupled together two or more cellulose acetate butyrate molecules and acrylic-multipolymer molecule as cross-bridge and forms the new compound macromole of bigger Mierocrystalline cellulose-multiple copolymer, and adopt the carboxyl reaction on organic polyamine and/or hydramine and the compound macromole, on macromolecular chain, introduce the side-chain radical that polar contains polyamines and/or hydroxyl.Two components of cellulose acetate butyrate and acrylic-multipolymer are to exist with cross-linked composite macromole form in the material that makes like this, and its intermiscibility is splendid, and mixture is also widened greatly to the choice of Solvent scope, and easily make more stable water miscible liquid.Though its water-resistance property of coating of filming than simple mixing method slightly reduces, its tensile strength, elasticity, anti-organic solvent etc. improve greatly, have comprehensive performance, and have overcome the plastic sense of acrylic resin well.
What below introduce is example as content of the present invention, and wherein example 1 and example 2 are to use by solvent-borne type, and example 3 is aqueous emulsion types.And introduced a simple mechanical hybrid system example in contrast.Obviously, the scope of the related theme of foregoing of the present invention is not limited only to these examples.Each routine material composition composition is seen attached list, and wherein the consumption of each composition is the parts by weight that calculate by pure substance, and total charging capacity of filling a prescription is 100 weight parts (not comprising initiator).
Example 1
The first step be routinely the free radical solution polymerization method to prepare acrylic-multipolymer stand-by.Second step will dissolve in solvent and the cellulose acetate butyrate input reactor, and dropped into the multiple copolymer mixing.Add linking agent down for 70～85 ℃ at normal pressure and temperature control, reacted 2.5～3 hours.Add organic polyamine and/or hydramine then, continue reaction 0.5～1 hour.Cooling drops into supplementary additive and abundant mixing, promptly obtains mother liquor.
Mother liquor is promptly obtained the solvent-borne type finished product after with the diluting solvent latting drown.This finished product outward appearance is faint yellow transparent liquid, and total solids level is about 28.4%, through place more than 1 year observe stablize not stratified.With its glued membrane that makes test, tensile strength 457Nf/cm
2, elongation at break 510%, permanentset value 7%, 24 hours water-intake rates of glued membrane immersion are 8.5%, toluene solvant immersion swelling ratio half an hour 145%.Glued membrane is with exposure in sunshine seven wheat harvesting periods, and its xanthochromia value only is 0.6.Final mean annual increment solution is covered with paint, lacquer, colour wash, etc. behind white leather top layer, and the observation feel is smooth careful, the tool low light level, and no plastic sense, fabulous with the bottom adhesion.
Example 2
The preparation method is with example 1.Finished product is a solvent-borne type, and outward appearance is a white solution.Total solids level 27.2%, finished fluid is stablized not stratified through depositing observation more than 6 months.Cover with paint, lacquer, colour wash, etc. behind white leather top layer, the observation feel is smooth careful, no plastic sense, and impression is pure whiter.
Example 3
Be aqueous emulsion type.The mother liquor preparation method is with example 1.Oil-soluble emulsifier is sneaked in the mother liquor, and stir into emulsion,, obtain the emulsion of appearance white again with colloidal mill or the contour dispersion treatment of high-shear emulsion machine with the water liquid that contains water soluble emulsifier.This liquid total solids level is about 19%, and emulsion was placed through 6 months and observed not breakdown of emulsion.Cover with paint, lacquer, colour wash, etc. behind white leather top layer, observe unglazed substantially, no plastic sense, surperficial feel is smooth careful, more similar solvent-borne type material is filmed more plentiful.
Reference examples
This example is a simple mechanical mixed solvent type.Multiple copolymer in its main film-forming components adopts the multiple copolymer of example 1, and cellulose acetate butyrate and various auxiliary interpolation materials and solvent types, content ratio are all identical with example 1, have only cancelled isocyanate-crosslinked component and side chain (organic polyamine) component.Prepared finished product is faint yellow transparent liquid, and total solids level is 28.1%.This liquid is placed not observe and just was divided into the two-layer of top look shallow bottom color depth in 5 months.This simple mechanical mixing solutions is made glued membrane test, its tensile strength 218Nf/cm
2, elongation at break 680%, permanentset value 42%, 24 hours water-intake rates of glued membrane immersion are 3.5%, soak less than 10 minutes just most of dissolved destructions in toluene, organic solvent resistance is very poor.Once tried to make water miscible liquid, all can not stablize maintenance one month behind this routine mother liquor adding blending emulsifiers.
Subordinate list:
Continuous table:
Claims (9)
1, a kind of by cellulose acetate butyrate and acrylic acid derivative, the vinyl monomer multiple copolymer is main film-forming components, and contain the solvent-borne type or the aqueous emulsion type coating material for leather of other auxiliary added ingredientss and tensio-active agent, it is characterized in that: carried out crosslinked with polyisocyanates between cellulose acetate butyrate molecule and the acrylic-multipolymer macromolecular chain, and part carboxyl on the multiple copolymer molecular chain and organic polyamine and/or alcamine compound reaction, generate amido linkage and introduced the polar side chain that contains polyamines and/or hydroxyl, wherein the weight ratio of cellulose acetate butyrate and acrylic-multipolymer is 0.05～1.5, the ratio of the mole number of hydroxyl is 0.1～1 on the polyisocyanate-based and main film-forming components, the mole dosage of organic polyamine and/or alcohol amine compound be in the main film-forming components carboxyl mole number 5～50%.
2, coating and decorating material according to claim 1 is characterized in that as linking agent the polyisocyanates of use has the fat chain structure to ultraviolet light stabilized.
3, coating and decorating material according to claim 1 and 2, it is characterized in that containing in the starting monomer of multiple copolymer part of synthetic its main film-forming components and be no less than 0.5% hydroxyl monomer, its consumption is 0.5～10% of a total monomer weight, and these hydroxyls of introducing the multiple copolymer molecular chain partly or entirely form amino-formate bond as cross-linking set and isocyanic ester radical reaction in final cross-linked composite.
4, coating and decorating material according to claim 1 and 2, it is characterized in that containing in the starting monomer of multiple copolymer part of synthetic its main film-forming components the monomer that is no less than 0.5% band carboxyl, its consumption is 0.5～8% of a total monomer weight, and these introduce carboxyl part and organic polyamine and/or alcohol amine compound reaction formation amido linkage in final cross-linked composite of multiple copolymer molecular chain.
5, coating and decorating material according to claim 1, the weight ratio that it is characterized in that cellulose acetate butyrate and acrylic-multipolymer is 0.1～1.
6, coating and decorating material according to claim 1 is characterized in that the ratio of the mole number of hydroxyl in polyisocyanate-based mole number and the main film-forming components is 0.3-0.8.
7, coating and decorating material according to claim 3 is characterized in that hydroxyl monomeric consumption is 1～8% of a starting monomer gross weight.
8, coating and decorating material according to claim 4 is characterized in that the monomeric consumption with carboxyl is 1～5% of a starting monomer gross weight.
9, coating and decorating material according to claim 1, the mole number that it is characterized in that organic polyamine and/or alcohol amine compound be in the main film-forming components carboxyl mole number 15～40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94111930A CN1055125C (en) | 1994-10-10 | 1994-10-10 | Acetate butyl fibre-propenoic acid composite leather coating and decorating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94111930A CN1055125C (en) | 1994-10-10 | 1994-10-10 | Acetate butyl fibre-propenoic acid composite leather coating and decorating material |
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| Publication Number | Publication Date |
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| CN1107171A true CN1107171A (en) | 1995-08-23 |
| CN1055125C CN1055125C (en) | 2000-08-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN94111930A Expired - Fee Related CN1055125C (en) | 1994-10-10 | 1994-10-10 | Acetate butyl fibre-propenoic acid composite leather coating and decorating material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088724C (en) * | 1999-05-18 | 2002-08-07 | 安徽大学恒泰精细化工公司 | Process for synthesizing aqueous emulsion of nitrocellulose-polyurethane and water-dilutable solution |
| CN102432777A (en) * | 2011-08-29 | 2012-05-02 | 华南理工大学 | Method for modifying cellulose acetate butyrate (CAB) for electro-silvered simulating coating |
| CN104877082A (en) * | 2015-06-02 | 2015-09-02 | 清远雅克化工有限公司 | Preparation method of CAB (cellulose acetate butyrate) graft modified hydroxy acrylic resin for electrosilvering paint |
| CN110628315A (en) * | 2019-10-10 | 2019-12-31 | 咸阳职业技术学院 | Green and environment-friendly leather finishing agent and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3785848A (en) * | 1969-09-04 | 1974-01-15 | Rohm & Haas | Polyurethane plasticized topcoat for leather and method |
| US4255298A (en) * | 1977-08-01 | 1981-03-10 | E. I. Du Pont De Nemours And Company | Acrylic graft copolymers and coating compositions thereof |
-
1994
- 1994-10-10 CN CN94111930A patent/CN1055125C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088724C (en) * | 1999-05-18 | 2002-08-07 | 安徽大学恒泰精细化工公司 | Process for synthesizing aqueous emulsion of nitrocellulose-polyurethane and water-dilutable solution |
| CN102432777A (en) * | 2011-08-29 | 2012-05-02 | 华南理工大学 | Method for modifying cellulose acetate butyrate (CAB) for electro-silvered simulating coating |
| CN104877082A (en) * | 2015-06-02 | 2015-09-02 | 清远雅克化工有限公司 | Preparation method of CAB (cellulose acetate butyrate) graft modified hydroxy acrylic resin for electrosilvering paint |
| CN110628315A (en) * | 2019-10-10 | 2019-12-31 | 咸阳职业技术学院 | Green and environment-friendly leather finishing agent and preparation method thereof |
| CN110628315B (en) * | 2019-10-10 | 2021-08-24 | 咸阳职业技术学院 | Green and environment-friendly leather finishing agent and preparation method thereof |
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| CN1055125C (en) | 2000-08-02 |
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