CN1861680A - Low fluorine content material and synthesizing process thereof - Google Patents
Low fluorine content material and synthesizing process thereof Download PDFInfo
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- CN1861680A CN1861680A CN 200610035300 CN200610035300A CN1861680A CN 1861680 A CN1861680 A CN 1861680A CN 200610035300 CN200610035300 CN 200610035300 CN 200610035300 A CN200610035300 A CN 200610035300A CN 1861680 A CN1861680 A CN 1861680A
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Abstract
This invention relates to a low fluorine material used for fabric treatment or paper, leather, wood, rock and other materials surface treatment and protection. It is a O/W type emulsion, includes fluorolkyl methacrylate or fuoroalkyl acrylate or both, acrylic ester or metharylate active or both, substitute ethylene with active radicals, modified monomeric random copolymerization, and the use of monomer with fluorine is below 20%. The method is also opened. This material not only makes protected materials acquire good property such as water proof, oil proof, anti-fouling, gas permeation, but also has ability of solvent resistance, acid resistance, alkali stability, and resistance to aging.
Description
Technical field
The present invention relates to a kind of waterproof that is used for textiles, grease proofing, antifouling, air-moisture-permeable arrangement or be used for the material of the surface treatment and the protection of paper, leather, timber, stone material and other material, the invention still further relates to the synthetic method of this material.
Background technology
It is the problem that people pay close attention to that the waterproof and oilproof of materials such as textiles, leather, paper, timber, stone material is handled always.Water-resisting agent mainly contains paraffin class, lipid acid triazines, silicone based, organic fluorine class, the less at present use of wherein preceding two classes, silicone based have excellent flexibility, hydrophobic effect very good, synthetic and industrialized producing technology is very ripe, cost is low, but not grease proofing, do not reach thoroughly antifouling requirement; Organic fluorine class water-resisting agent (especially acrylate containing fluorine polymkeric substance) not only has excellent waterproof, grease proofing and anti-pollution function, can also keep the original color and luster of material, if introduce feel and permeability that suitable comonomer can also be regulated material, and have extraordinary thermostability and chemical stability.
The research of fluorine-contained finishing agent starts from the thirties in 20th century, and Minnesota Mining and Manufacturing Company has at first synthesized low-molecular-weight voltalef (PCTFE), and and then the Plunkett of E.I.Du Pont Company invented the high-molecular weight polytetrafluoroethylene (PTFE) in 1938.Nineteen fifty, du pont company was published the patent of fluorine-contained finishing agent first, and nineteen fifty-three, Minnesota Mining and Manufacturing Company also developed its first-generation fluorine-contained finishing agent, and the sixties play states such as Japan, West Europe and also develop this series products in succession.China's research is in this respect started late, and the sixties, Chinese Academy of Sciences's organic chemistry institute and Shanghai City synthetic rubber institute began one's study, and each big scientific research institutions also progressively relates to this field after the nineties.The domestic exploitation that mainly concentrates on leather and paper usefulness water-resisting agent at present about the research of fluorine-containing water repellent, and the research of used for textiles fluorine-containing water repellent mainly concentrates on the research to external imported product application art at present, relevant independent development synthetic research is few, the fluorine-containing water repellent consumption that China is used for textile finishing is very big, and be the trend that rises year by year, but all be to use the product of external each major company basically.
Though the every performance of acrylate containing fluorine water-resisting agent is all fine but cost an arm and a leg, major cause is because acrylate containing fluorine monomer price height, the shared big cause of ratio of fluorochemical monomer when synthetic such fluorine material.According to recently relevant this class water-resisting agent synthetic patent, as US61221372, US6753376, EP1195420 etc., the consumption of fluorochemical monomer is all 50～80%.Therefore under the prerequisite that does not reduce its waterproof, performance such as grease proofing, antifouling; synthesize the low fluorine content material that not only can be used for the arrangement of textiles but also can be used for the surface treatment and the protection of paper, leather, timber, stone material and other material; thereby reduce cost, will have boundless market outlook.
Summary of the invention
The purpose of this invention is to provide a kind of waterproof, grease proofing, antifouling, air-moisture-permeable, high temperature resistant, acid and alkali-resistance, wash resistant, do not contain the low fluorine content material of organic solvent; this material both can be used for the arrangement of textiles, can be used for the surface treatment and the protection of paper, leather, timber, stone material and other material again.
Another object of the present invention provides the synthetic method of above-mentioned fluorine material, and this method technology is simple, the product yield height.
A kind of low fluorine content material that is used for textile finishing or paper, leather, timber, stone material and processing of other material surface and protection provided by the invention is a kind of O/W type emulsion, and its main component is fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid and composition thereof M
1, acrylate or methacrylic ester and composition thereof M
2, contain the substituted ethylene M of active group
3, modified monomer M
4Random copolymers, M wherein
1Consumption be 1～20%, M
2Consumption be 10～80%, M
3Consumption be 0.5～5%, M
4Consumption be 10～40%, and the consumption of fluorochemical monomer is lower than 20%, described percentage ratio is the mass percent that accounts for the total monomer consumption, its basic structure is:
Wherein: R
f=-C
mF
2m+1(m 〉=6); R
1=-C
pH
2p+1(p=1～20);
A=-COONHC
qH
2qOH (q=1～6), or-CN, or-COOC
rH
2rOH (r 〉=2)
-C
rH
2rCOOH (r 〉=0), or-C
nH
2nCONH
2(n 〉=0)
-Cl; X=-H or-CH
3
M
1Be the fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid and composition thereof, as vinylformic acid 17 fluorine octyl group ethyl esters etc.; M
2Be acrylate or methacrylic ester and composition thereof, as octadecyl acrylate etc.; M
3Be the substituted ethylene that contains active group, as methacrylic acid etc.; M
4Be modified monomer, as vinylbenzene etc.
The synthetic method of above-mentioned low fluorine content material provided by the invention is a free-radical emulsion polymerization, and concrete grammar is: under the room temperature with fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid and composition thereof M
1, acrylate or methacrylic ester and composition thereof M
2, contain the substituted ethylene M of active group
3, modified monomer M
4, emulsifying agent, molecular weight regulator, deionized water add in the reactor; install prolong, nitrogen conduit, agitator, thermometer, well heater; feed nitrogen and pre-emulsification 0.5～2 hour; heat temperature raising to 25～85 ℃; add initiator; insulation reaction 2～8 hours; be cooled to room temperature at last, obtain the low fluorine content material that low viscosity, flowable O/W type polymer emulsion are the waterproof that is used for textiles, grease proofing, antifouling, air-moisture-permeable arrangement or are used for the surface treatment and the protection of paper, leather, timber, stone material and other material.
In the above-mentioned synthetic method, emulsifying agent is an ionogenic surfactant, as sodium lauryl sulphate, Sodium palmityl sulfate, dodecylbenzene sodium sulfonate, trimethyldodecane base ammonium halide, trimethylammonium hexadecyl ammonium halide, triethyl dodecyl ammonium halide etc.; Or nonionic surface active agent, as OP series, Span and Tween series; Also can be their mixture, as the mixture of sodium lauryl sulphate and OP-10, the mixture of sodium lauryl sulphate and OP-4, the mixture of Sodium palmityl sulfate and OP-10, the mixture of Sodium palmityl sulfate and OP-4, the mixture of dodecylbenzene sodium sulfonate and OP-10, the mixture of dodecylbenzene sodium sulfonate and OP-4, the mixture of trimethylammonium hexadecyl ammonium halide and OP-10, the mixture of trimethylammonium hexadecyl ammonium halide and OP-4, the mixture of trimethyldodecane base ammonium halide and OP-10, the mixture of trimethyldodecane base ammonium halide and OP-4 etc.; The consumption of emulsifying agent accounts for 1～10% of total monomer consumption.
In the above-mentioned synthetic method, initiator is water-soluble persulphate, as K
2S
2O
8, Na
2S
2O
8, (NH
4)
2S
2O
8Deng; Or water soluble oxidized-reduction initiating system, as Na
2S
2O
3～K
2S
2O
8, NaHSO
3～(NH
4)
2S
2O
8, Na
2S
2O
3～(NH
4)
2S
2O
8, Na
2SO
3～(NH
4)
2S
2O
8, FeSO
4～(NH
4)
2S
2O
8, FeSO
4～K
2S
2O
8Deng; Or azo-initiator, as AIBN etc.; Or organic peroxy class initiator, as BPO etc.; The consumption of initiator accounts for 0.1～2% of total monomer consumption.
In the above-mentioned synthetic method, molecular weight regulator is a thio-alcohol, and as n-dodecane mercaptan etc., its consumption accounts for 0.1～2% of total monomer consumption.
The present invention is by introducing fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid and composition thereof monomer in multipolymer, can give the waterproof of the material excellence that is organized or protects, grease proofing, antifouling, breathable moisture permeability, and this material have anti-solvent, performance such as acidproof, alkaline-resisting, ageing-resistant; The substituted ethylene unit that contains active group in addition by introducing, make polymkeric substance under certain condition can with the material generation Chemical bond that is organized or protects, the crosslinked of appropriateness also can take place in material self, therefore the described material of this invention not only can be used for the material that there is the reactable group on the surface, also can be used for the material that the surface does not have the reactable group; Also just because of Chemical bond has taken place, so give the waterproof of material, grease proofing, antifouling, permeability wash resistant, resistance of rainwater washing against.Indication material of the present invention not only can be used for the arrangement of textiles, can also be used for the surface treatment or the protection of leather, paper, timber, stone material and other material.
The evaluating material of every performance of institute of the present invention synthetic low fluorine content material is the pure cotton woven fabric with this material processing.Water resistance is measured by the AATCC-22 method, is divided into 50,70,80,90,100 Pyatyis, and 100 is best; Oil preventing performance is measured by the AATCC-118 method, and is the highest 8 grades; Antifouling property is measured by the AATCC-130 method, and is the highest 5 grades; Permeability is pressed the GB/T12704-91 method and is measured; Washing resistance performance is estimated after 5 times and 20 times by 2g/L washing composition, 60 ℃ of washings; Acid-proof alkaline is pressed 10%NaOH solution and 2mol/L H respectively
2SO
4Soaking 1 hour afterwash estimates.
Compare with existing fluorine-containing water repellent, low fluorine content material of the present invention has the following advantages:
(1) low fluorine content material provided by the present invention is under the identical prerequisite of performance index, and fluorine content reduces greatly, thereby reduces production costs.
(2) it is multi-functional that this material integrates waterproof, grease proofing, antifouling, air-moisture-permeable, wash resistant etc.
(3) low fluorine content material provided by the present invention can not influence the original color of material, and feel can be regulated by the consumption of adjusting each comonomer as requested.
(4) synthetic low fluorine content material of the present invention is O/W type emulsion, and is easy to use, and do not contain organic solvent, to the environment friendliness.
(5) synthetic low fluorine content material of the present invention is widely used, and not only can be used for the multi-functional arrangement of textiles, also can be used for the surface treatment and the protection of paper, leather, timber, stone material and other material.
Embodiment
The present invention will be described to enumerate a part of specific embodiment below, is necessary to be pointed out that at this following specific embodiment only is used for that the invention will be further described, does not represent limiting the scope of the invention.Some nonessential modifications that other people make according to the present invention and adjustment still belong to protection scope of the present invention.Below all umbers be mass fraction, the fluorochemical monomer consumption is meant that fluorochemical monomer accounts for the mass percent of total monomer.
Embodiment 1
Under the room temperature with 18 parts of methyl methacrylates, 12 parts of butyl methacrylate, 15 parts of methacrylic acid stearyl, 12 parts of methacrylic acid ten difluoro heptyl esters, 2 parts of N-methylol third rare acyls, 1 part of vinylbenzene, 2 parts of sodium lauryl sulphate, 0.5 part n-dodecane mercaptan, 100 parts of deionized waters add in the reactor; Install prolong, nitrogen conduit, agitator, thermometer, well heater, pre-emulsification 1 hour; Feed nitrogen and heat temperature raising to 85 ℃, add 0.5 part of (NH
4)
2S
2O
8, insulation reaction 4 hours; Be cooled to room temperature at last, obtain flowable O/W type polymer emulsion and be this bright described fluorine material, its solid content is about 38.5%, and the fluorochemical monomer consumption is 19.2%.Every performance measurement the results are shown in Table 1.
Embodiment 2
With initiator 0.003mol NaHSO
3～(NH
4)
2S
2O
8(mol ratio 1: 1) replaces, and the insulation reaction temperature is 30 ℃, and the reaction times is 2 hours, and other raw material consumption is identical with embodiment 1 with operation steps.Every performance measurement the results are shown in Table 1.
Embodiment 3
Change the emulsifying agent among the embodiment 1 into 1 part of sodium lauryl sulphate and 1 part of OP-10, other raw material consumption, reaction conditions and operation steps are identical with embodiment 1.Every performance measurement the results are shown in Table 1.
Embodiment 4
Under the room temperature with 18 parts of methyl methacrylates, 12 parts of butyl acrylates, 15 parts of vinylformic acid stearyl, 10 parts of methacrylic acid perfluoro capryl ethyl esters, 3 parts of N-methylol third rare acyls, 5 parts of vinylchlorid, 2 parts of sodium lauryl sulphate, 0.5 part n-dodecane mercaptan, 100 parts of deionized waters add in the reactor; Install prolong, nitrogen conduit, agitator, thermometer, well heater, pre-emulsification 1.5 hours; Feed nitrogen and heat temperature raising to 45 ℃, add 0.0025mol Na
2S
2O
3～(NH
4)
2S
2O
8(mol ratio 1: 1), insulation reaction 2.5 hours; Be cooled to room temperature at last, obtain low viscosity, flowable O/W type polymer emulsion is fluorine material of the present invention, its solid content is about 39.2%, and the fluorochemical monomer consumption is 15.5%.Every performance measurement the results are shown in Table 1.
Embodiment 5
Initiator among the embodiment 4 is replaced with 0.2 part of azo diethyl butyronitrile (AIBN), and the insulation reaction temperature is 75 ℃, and the reaction times is 5 hours, and other raw material consumption is identical with embodiment 4 with operation steps.Every performance measurement the results are shown in Table 1.
Embodiment 6
Initiator among the embodiment 4 is replaced with 0.3 part of dibenzoyl peroxide (BPO), and the insulation reaction temperature is 80 ℃, and the reaction times is 5 hours, and other raw material consumption is identical with embodiment 4 with operation steps.Every performance measurement the results are shown in Table 1.
Embodiment 7
Under the room temperature with 20 parts of methyl acrylates, 15 parts of butyl methacrylate, 20 parts of dodecylacrylate, 15 parts of vinylformic acid perfluoro capryl ethyl esters, 3 parts of acrylamides, 5 parts of vinylchlorid, 2 parts of Propylene glycol monoacrylates, 3 parts of trimethyldodecane base brometo de amonios, 0.5 part octane mercaptan, 140 parts of deionized waters add in the reactor; Install prolong, nitrogen conduit, agitator, thermometer, well heater, pre-emulsification 1.5 hours; Feed nitrogen and heat temperature raising to 45 ℃, add 0.002mol Na
2S
2O
3～(NH
4)
2S
2O
8(mol ratio 1: 1), insulation reaction 3 hours; Be cooled to room temperature at last, obtain low viscosity, flowable O/W type polymer emulsion is fluorine material of the present invention, its solid content is about 37.4%, and the fluorochemical monomer consumption is 18.0%.Every performance measurement the results are shown in Table 1.
Embodiment 8
3 parts of trimethyldodecane base brometo de amonios among the embodiment 7 are replaced with the mixture of 2 parts of trimethyldodecane base brometo de amonios and a OP-4, and other raw material consumption, reaction conditions and operation steps are identical with embodiment 7.Every performance measurement the results are shown in Table 1.
Embodiment 9
Get 100 parts of methyl methacrylates, 80 parts of butyl acrylates, 100 parts of vinylformic acid stearyl, 60 parts of methacrylic acid perfluoro capryl ethyl esters, 15 parts of acrylamides, 25 parts of vinylchlorid, 10 parts of Hydroxyethyl acrylates, 10 parts of normal butane mercaptan, 20 parts of Span-80 and 20 parts of Tween-80 under the room temperature and be dissolved in mix monomer and 1200 parts of deionized waters respectively; Install prolong, nitrogen conduit, agitator, thermometer, well heater, the aqueous solution that will contain Tween-80 earlier adds in the reactor, under agitation adds the mix monomer that contains Span-80; Pre-then emulsification 1 hour; Feed nitrogen and heat temperature raising to 35 ℃, add 0.02mol NaHSO
3～K
2S
2O
8(mol ratio 1: 1), insulation reaction 2 hours; Be cooled to room temperature at last, obtain low viscosity, flowable O/W type polymer emulsion is fluorine material of the present invention, its solid content is about 26.8%, and the fluorochemical monomer consumption is 13.6%.Every performance measurement the results are shown in Table 1.
Embodiment 10
Get 24 parts of methyl methacrylates, 36 parts of ethyl propenoates, 10 parts of vinylformic acid stearyl, 20 parts of methacrylic dodecyl gallates, 25 parts of methacrylic acid perfluoro capryl ethyl esters, 2 parts of acrylamides, 5 parts of vinylchlorid, 2 parts of methacrylic acids, 1 part of n-dodecane mercaptan, 2 parts of Span-80 and 1.5 parts of sodium lauryl sulphate under the room temperature and be dissolved in mix monomer and 200 parts of deionized waters respectively; Install prolong, nitrogen conduit, agitator, thermometer, well heater, the aqueous solution that will contain sodium lauryl sulphate earlier adds in the reactor, under agitation adds the mix monomer that contains Span-80; Pre-then emulsification 0.5 hour; Feed nitrogen and heat temperature raising to 80 ℃, add 0.002mol K
2S
2O
8, insulation reaction 5 hours; Be cooled to room temperature at last, obtain low viscosity, flowable O/W type polymer emulsion is fluorine material of the present invention, its solid content is about 34.7%, and the fluorochemical monomer consumption is 19.2%.Every performance measurement the results are shown in Table 1.
The measurement result of embodiment 1～10 from table 1, the waterproof of low fluorine content material provided by the invention, grease proofing, antifouling, breathable moisture permeability is good, acid and alkali-resistance, wash resistant.
Table 1 embodiment 1～10 every performance measurement result
| The embodiment sequence number | Performance | |||||||||||||
| Before the washing | After washing 5 times | After washing 20 times | ||||||||||||
| To acid acceptance | To alkaline stability | Water-repellancy | Grease proofness | Didirtresistance | Ventilation property | Water-repellancy | Grease proofness | Didirtresistance | Ventilation property | Water-repellancy | Grease proofness | Didirtresistance | Ventilation property | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 | Unchanged unchanged | Unchanged unchanged | 80 80 90 100 90 90 90 90 80 100 | 5 grades 5 grades 5 grades 7 grades 7 grades 7 grades 8 grades 8 grades 6 grades 8 grades | 4 grades 4 grades 4 grades 4 grades 5 grades 5 grades 5 grades 5 grades 4 grades 5 grades | Unchanged unchanged slightly low slightly low slightly low slightly low | 90 90 90 100 100 100 100 100 80 100 | 5 grades 6 grades 6 grades 7 grades 7 grades 6 grades 8 grades 8 grades 6 grades 8 grades | 4 grades 4 grades 4 grades 4 grades 5 grades 5 grades 5 grades 5 grades 4 grades 5 grades | Unchanged unchanged slightly low slightly low slightly low slightly low | 80 80 80 90 90 90 100 100 80 100 | 5 grades 5 grades 5 grades 6 grades 7 grades 6 grades 8 grades 8 grades 5 grades 8 grades | 4 grades 4 grades 4 grades 4 grades 5 grades 4 grades 5 grades 5 grades 4 grades 5 grades | Unchanged unchanged |
Claims (7)
1. one kind is used for that textile finishing or paper, leather, timber, stone material and other material surface are handled and the low fluorine content material of protection; it is characterized in that: this low fluorine content material is a kind of O/W type emulsion, and its main component is fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid and composition thereof (M
1), acrylate or methacrylic ester and composition thereof (M
2), contain the substituted ethylene (M of active group
3), modified monomer (M
4) random copolymers, M wherein
1Consumption be 1～20%, M
2Consumption be 10～80%, M
3Consumption be 0.5～5%, M
4Consumption be 10～40%, and the consumption of fluorochemical monomer is lower than 20%, described percentage ratio is the mass percent that accounts for the total monomer consumption, its basic structure is:
Wherein: R
f=C
mF
2m+1(m 〉=6); R
1=-C
pH
2p+1(p=1～20);
A=-COONHC
qH
2qOH (q=1～6), or-CN, or-COOC
rH
2rOH (r 〉=2)
-C
rH
2rCOOH (r 〉=0), or-C
nH
2nCONH
2(n 〉=0)
-Cl; X=-H or-CH
3
2. the synthetic method of a low fluorine content material as claimed in claim 1 is characterized in that: with fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid and composition thereof (M
1), acrylate or methacrylic ester and composition thereof (M
2), contain the substituted ethylene (M of active group
3), modified monomer (M
4), emulsifying agent, molecular weight regulator, deionized water add in the reactor, install prolong, nitrogen conduit, agitator, thermometer, well heater, feed nitrogen and pre-emulsification 0.5～2 hour, heat temperature raising to 25～85 ℃, add initiator, insulation reaction 2～8 hours is cooled to room temperature at last, and obtaining low viscous O/W type polymer emulsion is low fluorine content material.
3. synthetic method according to claim 2 is characterized in that: described emulsifying agent is ionogenic surfactant, nonionic surface active agent or their mixture, and its consumption accounts for 1～10% of total monomer consumption.
4. synthetic method according to claim 3 is characterized in that: described ionogenic surfactant is sodium lauryl sulphate, Sodium palmityl sulfate, dodecylbenzene sodium sulfonate, trimethyldodecane base ammonium halide, trimethylammonium hexadecyl ammonium halide or triethyl dodecyl ammonium halide; Described nonionic surface active agent is OP series, Span or Tween series; The mixture of described ionogenic surfactant and nonionic surface active agent is the mixture of sodium lauryl sulphate and OP-10, the mixture of sodium lauryl sulphate and OP-4, the mixture of Sodium palmityl sulfate and OP-10, the mixture of Sodium palmityl sulfate and OP-4, the mixture of dodecylbenzene sodium sulfonate and OP-10, the mixture of dodecylbenzene sodium sulfonate and OP-4, the mixture of trimethylammonium hexadecyl ammonium halide and OP-10, the mixture of trimethylammonium hexadecyl ammonium halide and OP-4, the mixture of the mixture of trimethyldodecane base ammonium halide and OP-10 or trimethyldodecane base ammonium halide and OP-4.
5. synthetic method according to claim 2 is characterized in that: described initiator is water-soluble persulphate, water soluble oxidized-reduction initiating system, azo-initiator or organic peroxy class initiator, and its consumption accounts for 0.1～2% of total monomer consumption.
6. synthetic method according to claim 5 is characterized in that: described water-soluble persulphate is K
2S
2O
8, Na
2S
2O
8Or (NH
4)
2S
2O
8Described water soluble oxidized-reduction initiating is Na
2S
2O
3～K
2S
2O
8NaHSO
3～(NH
4)
2S
2O
8, Na
2S
2O
3～(NH
4)
2S
2O
8, Na
2SO
3～(NH
4)
2S
2O
8, FeSO
4～(NH
4)
2S
2O
8Or FeSO
4～K
2S
2O
8Described azo-initiator is AIBN; Described organic peroxy class initiator is BPO.
7. synthetic method according to claim 2 is characterized in that: described molecular weight regulator is the thio-alcohol molecular weight regulator, and its consumption accounts for 0.1～2% of total monomer consumption.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100353009A CN100523078C (en) | 2006-04-29 | 2006-04-29 | Low fluorine content material and synthesizing process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1861680A true CN1861680A (en) | 2006-11-15 |
| CN100523078C CN100523078C (en) | 2009-08-05 |
Family
ID=37389217
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108109A (en) * | 2010-12-29 | 2011-06-29 | 四川理工学院 | Preparation method of fluorine-containing fabric finishing agent |
| CN108611858A (en) * | 2018-05-07 | 2018-10-02 | 佛山慧创正元新材料科技有限公司 | A kind of resistance to waterproof coating gluing finishing agent used for textiles and preparation method thereof washed by force |
| CN108823995A (en) * | 2018-07-04 | 2018-11-16 | 北京汽车研究总院有限公司 | Artificial leather inorganic agent, artificial polyvinyl chloride leather, preparation method and the usage |
| CN113373726A (en) * | 2021-05-27 | 2021-09-10 | 珠海红塔仁恒包装股份有限公司 | Latex and preparation method and application thereof |
-
2006
- 2006-04-29 CN CNB2006100353009A patent/CN100523078C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108109A (en) * | 2010-12-29 | 2011-06-29 | 四川理工学院 | Preparation method of fluorine-containing fabric finishing agent |
| CN108611858A (en) * | 2018-05-07 | 2018-10-02 | 佛山慧创正元新材料科技有限公司 | A kind of resistance to waterproof coating gluing finishing agent used for textiles and preparation method thereof washed by force |
| CN108823995A (en) * | 2018-07-04 | 2018-11-16 | 北京汽车研究总院有限公司 | Artificial leather inorganic agent, artificial polyvinyl chloride leather, preparation method and the usage |
| CN113373726A (en) * | 2021-05-27 | 2021-09-10 | 珠海红塔仁恒包装股份有限公司 | Latex and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100523078C (en) | 2009-08-05 |
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