CN103628316A - Novel preparation method of paper fiber fabric coating finishing agent microemulsion - Google Patents
Novel preparation method of paper fiber fabric coating finishing agent microemulsion Download PDFInfo
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Abstract
The invention discloses a novel preparation method of paper fiber fabric coating finishing agent microemulsion. The novel preparation method comprises the following steps of: preparing semi-transparent polymer micro latex by adopting a semi-continuous seed microemulsion polymerization method; carrying out ammoniation reaction and high-speed shearing dispersion to obtain aqueous polyacrylate microemulsion. Latex particles are regularly spherical and have particle diameter of 30 nanometers-100 nanometers. Microemulsion solid content is 40% and dosage of an emulsifier is less than 2%. According to the invention, a reaction thermodynamic system for microemulsion polymerization is stable, and dispersion phase dimension is smaller; by virtue of the method, particle diameter of the polymer emulsion is small, particle size distribution is uniform and emulsion performances are stable. Waterproof permeability, durability, practicability and aesthetic sense of the fabric treated by the developed coating finishing agent are greatly improved, so that expected application effect is achieved.
Description
Technical field
The present invention relates to chemistry and field of material preparation, especially relate to the Novel paper fabric coating finishing agent microemulsion preparation method of a kind of high solids content, low emulsifier.
Background technology
Solve intrinsic low, the easy water suction of intensity of paper fabric, easily go mouldy, the key of the shortcoming such as gloss difference carries out top finish to paper fabric exactly, by the use of special coating finishing agent, to give its different performance.
Polyacrylate fabric coating finishing agent is mainly made by adding different auxiliary agent allotments by polyacrylate dispersion.Polyacrylate dispersion polymerization system is mainly comprised of monomer, water soluble starter (as ammonium persulfate, potassium peroxydisulfate), emulsifying agent and 4 kinds of bases of water.In polymerization formula system, can, according to different top finish effect requirements, introduce particular monomers and different technique, to meet different Functional Requirements.
Chinese invention patent CN1502635A discloses a kind of modified polyacrylate microemulsion and synthetic method thereof, and this synthetic method is specifically by three steps: the 1) pre-emulsification of nuclear monomer; 2) pre-emulsification of shell monomer; 3) by hud polymerization method, carry out polymerization.The modified polyacrylate microemulsion obtaining consists of: solid content 28～34wt%, and emulsifier content 2～3wt%, cosurfactant 3～4wt%, particle diameter is less than 100nm.United States Patent (USP) wO9634699, a kind of novel microemulsion technology of preparing is disclosed, by adopting styrene or cinnamic derivative and the copolymerization of (methyl) acrylate monomer, the emulsifying agent adopting is the soluble copolymer containing acid functional group of a kind of low molecular weight alkali, make a kind of microemulsion, with this microemulsion, mix with starch, obtain the finishing agent that a kind of paper surface is used.United States Patent (USP) WO2004037867 discloses a kind of by microemulsion technology, the technology that adopts unsaturated vinyl monomer to synthesize microemulsion, and it can be used for textiles, leather, paper.China's published article waits in " the synthetic and self-crosslinking performance study of microemulsion coating agent " literary composition of delivering in < < printing and dyeing > > the 7th phase in 1997, synthesized polyacrylate microemulsion self-crosslinking coating finishing agent, studied self-cross linking monomer consumption to coated film resistance to water, the impact of tensile property on coated fabric resistance to hydrostatic pressure; The microemulsion good film-forming property, the film forming gloss that make are high, smooth, soft, the novel fabric coating agent of easy to use and safety non-pollution.
These acrylic microemulsions above, solid content is lower, and solid content increases, and its viscosity will increase, and makes its microemulsion being synthesized, and is restricted in the use, and emulsifier is large, and it is more consuming time than common emulsion when synthetic, consumption power, power consumption source.
Summary of the invention
The object of this invention is to provide a kind of novel paper fabric coating finishing agent microemulsion preparation method, solving low, the easy water suction of existing paper fibre strength, easily go mouldy, the problem such as gloss difference.
To achieve these goals, the present invention adopts following technical scheme:
A novel paper fabric coating finishing agent microemulsion preparation method, it comprises the following steps:
(1) prepare translucent micro polymer latex:
1) deionized water (deionized water account for raw material gross weight 45～55%) of raw material 45～55.5wt% will be accounted for, the emulsifying agent of 0.7～1.8wt% (emulsifying agent account for raw material gross weight 0.7～1.8%), the molecular weight regulator of 0.05～0.22wt% (molecular weight regulator account for raw material gross weight 0.05～0.22%), the initiator A of the pH buffer of 0.1～0.3wt% (pH buffer account for raw material gross weight 0.1～0.3%) and 0.2～0.6wt% (initiator A account for raw material gross weight 0.2～0.6%) is placed in polymer reactor, continue again logical nitrogen 3～5min, stir simultaneously and heat,
2) take account for raw material 38～45wt% oil-soluble monomer in monomer groove A;
3) take account for raw material 0.6～5wt% water-soluble monomer in monomer dropping groove B;
4) taking in addition the initiator B that accounts for raw material 0.1-0.21wt% is diluted with water to after the mass concentration of 1.5%-2.5% (preferred mass concentration is 2%), be placed in initator dropwise adding tank, when temperature rises to 70～80 ℃ in polymer reactor, start to drip water-soluble monomer and oil-soluble monomer;
5) control reaction temperature between 70～90 ℃, oil-soluble monomer and water-soluble oil soluble monomers and water-soluble monomer dropwise in 3～5h, and the initiator solution of initator dropwise adding tank is added once for 1 hour, and 3～4h adds end;
6) after treating that all batchings drip and finish, after insulation a period of time, carry out cooling, through filtration discharging,
Obtain translucent micro polymer latex;
(2) prepare water polyacrylic acid microemulsion: the ammonia spirit that is 25～30% in translucent micro polymer latex dropping mass concentration is to microemulsion, regulate pH to 7-8, then after disperseing by high shear dispersion machine high speed shear, obtain the water polyacrylic acid microemulsion of transparent clear;
(3) preparation of paper fabric finishing agent: the water polyacrylic acid microemulsion that step (2) is obtained adds flexibilizer, microcapsule anti-bacterial agent, makes the finished product of transparent clear after fully stirring except mite agent, defoamer;
Wherein, the described raw material in step (1) comprises: deionized water, emulsifying agent, molecular weight regulator, pH buffer, initiator A, B, oil-soluble monomer, water-soluble monomer, and the material quality percentage sum consisting of each component is 100%.
In a kind of novel paper fabric coating finishing agent microemulsion preparation method described in preferred embodiment of the present invention, described oil-soluble monomer is the mixture between one or more in alkyl acrylate, alkyl methacrylate, vinyl aromatic compounds.
In a kind of novel paper fabric coating finishing agent microemulsion preparation method described in preferred embodiment of the present invention, described alkyl acrylate is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, Isooctyl acrylate monomer or 2-EHA;
Described alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, n octyl methacrylate or EHMA;
Described vinyl aromatic compounds is styrene, methyl styrene, chlorostyrene, t-butyl styrene or dimethyl styrene.
In a kind of novel paper fabric coating finishing agent microemulsion preparation method described in preferred embodiment of the present invention, described water-soluble monomer is acrylamide, N, the composition between one or more in N-2 methylol acryloyl ammonium, N hydroxymethyl acrylamide NMA, N-methylol methacrylamide or methacrylic acid MAA.
In a kind of novel paper fabric coating finishing agent microemulsion preparation method described in preferred embodiment of the present invention, described emulsifying agent is that primary emulsion and assistant for emulsifying agent collocation are made, the ratio of collocation is that the ratio of primary emulsion and assistant for emulsifying agent is 3: 1～5: 1, and the consumption of this emulsifying agent accounts for the 0.5%-2% of water-soluble monomer and oil-soluble monomer gross weight.
In a kind of novel paper fabric coating finishing agent microemulsion preparation method described in preferred embodiment of the present invention,
Described primary emulsion is alkylamide vinyl sulfonic acid sodium, neopelex or lauryl sodium sulfate;
Described assistant for emulsifying agent is normal propyl alcohol, n-butanol, n-amyl alcohol or n-hexyl alcohol.
In a kind of novel paper fabric coating finishing agent microemulsion preparation method described in preferred embodiment of the present invention, described initiator A, B are potassium peroxydisulfate, sodium peroxydisulfate or ammonium persulfate, and its total consumption is the 1%-5% of water-soluble monomer and oil-soluble monomer gross weight.
In a kind of novel paper fabric coating finishing agent microemulsion preparation method described in preferred embodiment of the present invention, described molecular weight regulator is tertiary lauryl mercaptan or n-dodecyl mercaptan, and its addition accounts for the 0.05%-0.5% of water-soluble monomer and oil-soluble monomer gross weight.
In a kind of novel paper fabric coating finishing agent microemulsion preparation method described in preferred embodiment of the present invention, the pH buffer of micro-emulsion polymerization is sodium bicarbonate or sodium dihydrogen phosphate.
In a kind of novel paper fabric coating finishing agent microemulsion preparation method described in preferred embodiment of the present invention, in step (1), feed way is the synchronous technique dripping of water-soluble monomer and oil-soluble monomer, and twice drips interval time is 0.5h-1.5h.
The present invention has following beneficial effect:
(1) the present invention can obtain solid content up to 40%, the microemulsion that emulsifier content is less than 2%.
(2) adopt and be different from conventional micro-emulsion polymerization technique, make water-soluble monomer be wrapped in all the time polymer beads sub-surface, form " aquation protective layer ", improved the stability of micro-emulsion polymerization.
(3) utilize synthetic polyacrylic acid microemulsion finishing agent to arrange paper fabric, overcome intrinsic low, the easy water suction of intensity of paper fiber, easily go mouldy, the shortcoming such as gloss difference, improved the quality of paper fabric goods.
Accompanying drawing explanation
Fig. 1 is polyacrylic ester microemulsion particle diameter distribution map.
Fig. 2 is polyacrylic ester microemulsion molecular weight and distribution map.
Fig. 3 is the TEM figure of polyacrylic ester microemulsion.
Fig. 4 is the FTIR spectrogram of Microemulsion Polymer.
Fig. 5 is the DSC figure of Microemulsion Polymer.
The specific embodiment
For technological means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below in conjunction with concrete diagram, further set forth the present invention.
Embodiment 1:
Step 1: micro-emulsion polymerization (preparing translucent micro polymer latex)
Take 600g gram of deionized water, 8g gram emulsifying agent, 1g molecular weight regulator, 1.5gpH buffer (such as sodium bicarbonate) and 2.96g initiator A in polymer reactor, logical N
2gas 5min, starts and stirs and open heating.Take butyl acrylate 86g, methyl methacrylate 178g, styrene 200g is in monomer groove A; Take a certain amount of methacrylic acid (MAA) water-soluble monomer 9.46g, and with the water-soluble solution of 50g, be placed in monomer dropping groove B.Take in addition initiator B 2g with after the dilution of 200g water, be placed in initator dropwise adding tank, treat that in polymer reactor, temperature rises to 75～78 ℃, drip water-soluble monomer and oil-soluble monomer, feed way is the synchronous technique dripping of water-soluble monomer and oil-soluble monomer, control reaction temperature between 78-82 ℃, oil-soluble monomer and water-soluble monomer dropwise in 4～5h, be controlled at 0.5h-1.5h and be advisable the interval time of twice dropping, initiator solution is approximately added once for every 1 hour, within 4～5 hours, adds end.Until all gobs, add after end, in 80～85 ℃ of insulation 60min, after finishing, be cooled to below 50 ℃, filter discharging, obtain translucent micro polymer latex.
Wherein, Fig. 4 shows the FTIR spectrogram of Microemulsion Polymer; Fig. 5 is the DSC figure of Microemulsion Polymer.
In step 1, emulsifying agent comprises primary emulsion and assistant for emulsifying agent, and the two blend proportion is 3: 1～5: 1, and primary emulsion includes but not limited to alkylamide vinyl sulfonic acid sodium, neopelex or lauryl sodium sulfate; Assistant for emulsifying agent includes but not limited to normal propyl alcohol, n-butanol, n-amyl alcohol or n-hexyl alcohol.
Step 2: aminating reaction (preparing water polyacrylic acid microemulsion):
Above-mentioned microemulsion (the resulting micro polymer latex of step 1) is dripped under the stirring of 60-70 ℃ strong (what strongly refer to is that the speed of the frequency that stirs and disturbance is higher) to mass concentration here and is 28% ammonia spirit, regulate pH to 7～8, then disperse rear translucent fine latex to become the glue (being water polyacrylic acid microemulsion) of transparent clear by high shear dispersion machine high speed shear.
Wherein, Fig. 1 shows polyacrylic ester microemulsion particle diameter distribution map; Fig. 2 shows polyacrylic ester microemulsion molecular weight and distribution map; Fig. 3 shows the TEM figure of polyacrylic ester microemulsion microemulsion.
Step 3: the preparation of paper fabric finishing agent
The limpid microemulsion of making through step 1, step 2 (water polyacrylic acid microemulsion) adds appropriate flexibilizer, microcapsule anti-bacterial agent, after fully stirring, makes the microemulsion paper fabric finishing agent of transparent clear except mite agent, defoamer, wherein, flexibilizer, microcapsule anti-bacterial agent, add overall control in 0.1～2% of microemulsion paper fabric finishing agent gross weight except mite agent, defoamer.
Buy and execute example 2:
Step 1: micro-emulsion polymerization (preparing translucent micro polymer latex)
Take 560g gram of deionized water, 7.5g gram emulsifying agent, 2.1g molecular weight regulator, 1.5gpH buffer (such as sodium dihydrogen phosphate) and 2.9g initiator A in polymer reactor, logical N2 gas 5min, starts and stirs and open heating.Take butyl acrylate 92g, methyl methacrylate 160g, styrene 190g is in monomer groove A; Take a certain amount of methacrylic acid water-soluble monomer 7.0g, and with the water-soluble solution of 50g, be placed in monomer dropping groove B.Take in addition initiator B 2g with after the dilution of 200g water, be placed in initator dropwise adding tank, treat that in polymer reactor, temperature rises to 75～78 ℃, synchronous water-soluble monomer and the oil-soluble monomer of dripping, control reaction temperature between 78-82 ℃, oil-soluble monomer and water-soluble monomer dropwise in 4～5h, and be controlled at 0.5h-1.5h and be advisable the interval time of twice dropping, initiator B solution is approximately added once for every 1 hour, within 4～5 hours, adds end.Until all gobs, add after end, in 80～85 ℃ of insulation 60min, after finishing, be cooled to below 50 ℃, filter discharging, obtain translucent micro polymer latex.
Step 2: aminating reaction (preparing water polyacrylic acid microemulsion):
Above-mentioned microemulsion is dripped to ammonia spirit under 60-70 ℃ of strong stirring, regulate pH to 7～8, translucent fine latex becomes the glue of transparent clear.
Step 3: the preparation of paper fabric finishing agent
The limpid microemulsion that step 1, step 2 are made adds appropriate flexibilizer, microcapsule anti-bacterial agent, after fully stirring, makes the microemulsion paper fabric finishing agent of transparent clear except mite agent, defoamer.
Embodiment 3: step 1: micro-emulsion polymerization (preparing translucent micro polymer latex)
Take 520g gram of deionized water, 7.0g gram emulsifying agent, 2.1g molecular weight regulator, 2.0gpH buffer (such as sodium bicarbonate) and 2.5g initiator A in polymer reactor, logical N2 gas 5min, starts and stirs and open heating.Take butyl acrylate 92g, methyl methacrylate 150g, styrene 200g is in monomer groove A; Take a certain amount of methacrylic acid water-soluble monomer 7.0g, and with the water-soluble solution of 50g, be placed in monomer dropping groove B.Take in addition initiator B 2g with after the dilution of 200g water, be placed in initator dropwise adding tank, treat that in polymer reactor, temperature rises to 75～78 ℃, synchronous water-soluble monomer and the oil-soluble monomer of dripping, control reaction temperature between 78-82 ℃, oil-soluble monomer and water-soluble monomer dropwise in 4～5h, and be controlled at 0.5h-1.5h and be advisable the interval time of twice dropping, initiator B solution is approximately added once for every 1 hour, within 4～5 hours, adds end.Until all gobs, add after end, in 80～85 ℃ of insulation 60min, after finishing, be cooled to below 50 ℃, filter discharging, obtain translucent micro polymer latex.
Step 2: aminating reaction (preparing water polyacrylic acid microemulsion):
Above-mentioned microemulsion is dripped to ammonia spirit under 60-70 ℃ of strong stirring, regulate pH to 7～8, translucent fine latex becomes the glue of transparent clear.
Step 3: the preparation of paper fabric finishing agent
The limpid microemulsion that step 1, step 2 are made adds appropriate flexibilizer, microcapsule anti-bacterial agent, after fully stirring, makes the microemulsion paper fabric finishing agent of transparent clear except mite agent, defoamer.
It should be noted that, water-soluble monomer given situation, can also adopt following situation: water-soluble monomer is the mixed solution of N hydroxymethyl acrylamide NMA and methacrylic acid MAA in previous embodiment.
This case adopts semi-continuous seed microemulsion polymerization method to make translucent micro polymer latex, and aminating reaction high speed shear obtain water polyacrylic acid microemulsion after disperseing.Latex particle is regular spherical, particle diameter in 30～100 nanometers.Microemulsion solid content is reaching 40%, and emulsifier is less than 2%.The thermodynamics of reactions stable system of micro-emulsion polymerization in the present invention, dispersed phase size is less, and the method can make the particle diameter of polymer emulsion little, even particle size distribution, emulsion property is stable.Fabric after developed coating finishing agent is processed, its water-proof breathable properties, durability, practicality, aesthetic property improve greatly, have reached the effect of expection.
Claims (10)
1. a novel paper fabric coating finishing agent microemulsion preparation method, is characterized in that, it comprises the following steps:
(1) prepare translucent micro polymer latex:
1) deionized water of raw material 45～55.5wt% will be accounted for, the pH buffer of the molecular weight regulator of the emulsifying agent of 0.7～1.8wt%, 0.05～0.22wt%, 0.1～0.3wt% and the initiator A of 0.2～0.6wt% are placed in polymer reactor, continue again logical nitrogen 3～5min, stir simultaneously and heat;
2) take account for raw material 38～45wt% oil-soluble monomer in monomer groove A;
3) take account for raw material 0.6～5wt% water-soluble monomer in monomer dropping groove B;
4) take in addition the initiator B that accounts for raw material 0.1-0.21wt% and be diluted with water to after the mass concentration of 1.5%-2.5%, be placed in initator dropwise adding tank, when temperature rises to 70～80 ℃ in polymer reactor, start to drip water-soluble monomer and oil-soluble monomer;
5) control reaction temperature between 70～90 ℃, oil-soluble monomer and water-soluble monomer dropwise in 3～5h, and the initiator B solution of initator dropwise adding tank is added once for 1 hour, and 3～4h adds end;
6) after treating that all batchings drip and finish, after insulation a period of time, carry out coolingly, through filtering discharging, obtain translucent micro polymer latex;
(2) prepare water polyacrylic acid microemulsion: the ammonia spirit that is 25～30% in translucent micro polymer latex dropping mass concentration is to microemulsion, regulate pH to 7-8, then after disperseing by high shear dispersion machine high speed shear, obtain the water polyacrylic acid microemulsion of transparent clear;
(3) preparation of paper fabric finishing agent: the water polyacrylic acid microemulsion that step (2) is obtained adds flexibilizer, microcapsule anti-bacterial agent, makes the finished product of transparent clear after fully stirring except mite agent, defoamer;
Wherein, the described raw material in step (1) comprises: deionized water, emulsifying agent, molecular weight regulator, pH buffer, initiator A, B, oil-soluble monomer, water-soluble monomer, and the material quality percentage sum consisting of each component is 100%.
2. a kind of novel paper fabric coating finishing agent microemulsion preparation method according to claim 1, it is characterized in that, described oil-soluble monomer is the mixture between one or more in alkyl acrylate, alkyl methacrylate, vinyl aromatic compounds.
3. a kind of novel paper fabric coating finishing agent microemulsion preparation method according to claim 2, is characterized in that,
Described alkyl acrylate is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, Isooctyl acrylate monomer or 2-EHA;
Described alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, n octyl methacrylate or EHMA;
Described vinyl aromatic compounds is styrene, methyl styrene, chlorostyrene, t-butyl styrene or dimethyl styrene.
4. a kind of novel paper fabric coating finishing agent microemulsion preparation method according to claim 1, it is characterized in that, described water-soluble monomer is acrylamide, N, the composition between one or more in N-2 methylol acryloyl ammonium, N hydroxymethyl acrylamide NMA, N-methylol methacrylamide or methacrylic acid MAA.
5. a kind of novel paper fabric coating finishing agent microemulsion preparation method according to claim 1, it is characterized in that, described emulsifying agent is that primary emulsion and assistant for emulsifying agent collocation are made, the ratio of collocation is that the ratio of primary emulsion and assistant for emulsifying agent is 3: 1～5: 1, and the consumption of this emulsifying agent accounts for the 0.5%-2% of water-soluble monomer and oil-soluble monomer gross weight.
6. a kind of novel paper fabric coating finishing agent microemulsion preparation method according to claim 5, is characterized in that,
Described primary emulsion is alkylamide vinyl sulfonic acid sodium, neopelex or lauryl sodium sulfate;
Described assistant for emulsifying agent is normal propyl alcohol, n-butanol, n-amyl alcohol or n-hexyl alcohol.
7. a kind of novel paper fabric coating finishing agent microemulsion preparation method according to claim 1, it is characterized in that, described initiator A, B are potassium peroxydisulfate, sodium peroxydisulfate or ammonium persulfate, and its total consumption is the 1%-5% of water-soluble monomer and oil-soluble monomer gross weight.
8. a kind of novel paper fabric coating finishing agent microemulsion preparation method according to claim 1, it is characterized in that, described molecular weight regulator is tertiary lauryl mercaptan or n-dodecyl mercaptan, and its addition accounts for the 0.05%-0.5% of water-soluble monomer and oil-soluble monomer gross weight.
9. a kind of novel paper fabric coating finishing agent microemulsion preparation method according to claim 1, is characterized in that, the pH buffer of micro-emulsion polymerization is sodium bicarbonate or sodium dihydrogen phosphate.
10. a kind of novel paper fabric coating finishing agent microemulsion preparation method according to claim 1, it is characterized in that, in step (1), feed way is the synchronous technique dripping of water-soluble monomer and oil-soluble monomer, and twice drips interval time is 0.5h-1.5h.
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| CN105368418A (en) * | 2015-12-11 | 2016-03-02 | 西南石油大学 | Coconut charcoal fiber flexibilizer for improving mechanical properties of well-cementing cement |
| CN106237946A (en) * | 2016-08-08 | 2016-12-21 | 湖北金民纤维材料科技有限公司 | A kind of microcapsule adapting to Deinking Pulp carbon-free body paper coating carbonless paper and production technology thereof |
| CN108498842A (en) * | 2018-05-15 | 2018-09-07 | 东莞市联洲知识产权运营管理有限公司 | A kind of medical dressing and preparation method thereof for external Wound care |
| CN108951111A (en) * | 2018-06-06 | 2018-12-07 | 苏州印丝特纺织数码科技有限公司 | A kind of antistatic finishing agent and preparation method thereof for dacron |
| CN110541301A (en) * | 2018-05-28 | 2019-12-06 | 句容市华冠服帽厂 | Microemulsion containing acaricide, preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105368418A (en) * | 2015-12-11 | 2016-03-02 | 西南石油大学 | Coconut charcoal fiber flexibilizer for improving mechanical properties of well-cementing cement |
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| CN108498842A (en) * | 2018-05-15 | 2018-09-07 | 东莞市联洲知识产权运营管理有限公司 | A kind of medical dressing and preparation method thereof for external Wound care |
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| CN110541301A (en) * | 2018-05-28 | 2019-12-06 | 句容市华冠服帽厂 | Microemulsion containing acaricide, preparation method and application thereof |
| CN108951111A (en) * | 2018-06-06 | 2018-12-07 | 苏州印丝特纺织数码科技有限公司 | A kind of antistatic finishing agent and preparation method thereof for dacron |
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Application publication date: 20140312 |