CN104147987A - Preparation method for microcapsules coating air-drying film forming material - Google Patents
Preparation method for microcapsules coating air-drying film forming material Download PDFInfo
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- CN104147987A CN104147987A CN201410381319.3A CN201410381319A CN104147987A CN 104147987 A CN104147987 A CN 104147987A CN 201410381319 A CN201410381319 A CN 201410381319A CN 104147987 A CN104147987 A CN 104147987A
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Abstract
A preparation method for microcapsules coating an air-drying film forming material comprises the following steps: a) mixing an additive and water to prepare an additive water solution; b) uniformly mixing a capsule-core material and a reactive monomer which is used for preparing a capsule-wall material; c) adding the mixture prepared in Step b into the additive water solution prepared in Step a, and conducting mechanical dispersion to form stable dispersion liquid; d) adding an amine material, and conducting interfacial reaction to form the microcapsules; e) filtering, washing and drying the prepared microcapsules. According to the preparation method provided by the invention, heating is scarcely needed in the microcapsule preparation process, so that energy is saved, the energy consumption is low, the technology is simple, and the operation is convenient; besides, as interfacial polymerization reaction occurs on an oil-water surface and is different from in-situ polymerization, which forms a wall material by virtue of accumulation, the surfaces of the microcapsules are smoother relatively. The microcapsules are applied to coatings to realize self-healing of damaged parts, and prolong the service lives of the coatings.
Description
Technical field
The invention belongs to paint field, particularly a kind of preparation method of the microcapsules that are applied to the coated self-drying type film forming matter in coating.
Background technology
Coating is mainly in order to protect object surface, but coating inevitably can produce damage under extraneous effect, if damage location can not be repaired in time, will make the performance of film greatly reduce.20th century the mid-80, the concept of self-healing is proposed first by US military.Self-healing technology is the characteristic of mimic biology structure, realizes material and realize under the condition that there is no external condition or have the external condition of little easy realization to participate in the oneself healing of material, and self-healing technology is highly profitable to the easy to use of coating.The self-healing function of coating became the focus of research in recent years.
Microcapsules technology is the most effectively to realize the technology of material self-healing at present, is a kind of resist technology, and it adopts filmogen that some are had to reactivity, sensitiveness or volatile liquid or solid and seals formation fine particle.This technology starts from the thirties in last century, start to be most applied to NCR, along with deepening continuously of microcapsules technology research, the application of microcapsules technology, also in continuous expansion, is applied in fields such as medicine, agricultural chemicals, food, cosmetics, building, bioengineering at present to some extent.Along with microcapsules are applied to the development of self-healing technology, a kind of component of people using the microcapsules that contain renovation agent as coating, makes the coating can self-healing in the time sustaining damage, thereby extends the life-span of coating.
The people such as White have prepared the microcapsules of Lauxite coating dicyclopentadiene by situ aggregation method, realize self-healing (S.R.White, N.R.Sottos, the P.H.Geubelle of epoxy resin composite material, J.S.Morre, M.R.Kessler, S.R.Sriram, E.N.Brown and S.Vis, Nature, 2001,409,794-797).White team (Brown E N, White S R, Sottos N R, Microcapsule induced toughening in a self-healing polymer composites, Journal of materials science, 2004,39 (5): 1703-1710, Brown E N, White S R, Sottos N R, Retardation and repair of fatigue cracks in microcapsule toughened epoxy composite-Part 1:manual infiltration, Composites science and technology, 2005, 65 (15): 2466-2473) to microcapsules in self-healing material, should be used as a large amount of research, and the several factors that affect material remediation efficiency are inquired into, show that by research under the suitable process conditions of being added in of microcapsules, remediation efficiency can reach 90%.Blaiszik (Blaiszik B J, Caruso M M, Mcllroy D A, et al, Microcapsules filled with reactive solutions for self-healing materials, Polymer, 2009, 50:990-997), Li Yuan (Li Yuan, Aijuan Gu, Guozheng Liang, Preparation and properties of poly (urea-formaldehyde) microcapsules filled with epoxy resins, Materials Chemistry and physics, 2008, 110:417-425) etc. Lauxite parcel epoxy resin and solvent are realized to self-healing and done a series of research.
Suryanarayana (Suryanarayana C, Chowdodj R K, Dhirendra K.Prepration and characterization of microcapsules containing linseed oil and its use in self-healing coatings, Progress in organic coatings, 2008, 63:72-78), Samadzadeh (Samadzadeh M, Hatami B S, Peikari M, et al.Tung oil:An autonomous repairing agent for self-healing epoxy coatings, Progress in organic coatings, 2011, 70:383-387) etc. people adopts respectively one-step method to prepare and wraps up semi-drying with Lauxite, the microcapsules of drying oil are for the self-healing of coating, the Microcapsules Size of preparation is about 40-400 micron.
The people such as Jiang Meijia have studied melamine-formaldehyde two-step method and have prepared self-drying type film forming matter microcapsules, preparation technology has been carried out to comparatively deep research (Jiang Meijia, Wang Shengzao, all rice rice etc., be applied to the research of microcapsule preparation process in self-healing coating, China's coating, 2014,29:21-26).
What described microcapsule preparation process all adopted above is in-situ polymerization technique, and main raw material(s) comprises harmful formaldehyde, and technique length consuming time, operates complicated.No matter be that urea-formaldehyde one-step method is prepared microcapsules, or the microcapsules prepared of melamine-formaldehyde method, all need to provide heat energy, under hot conditions, react, and can remaining unreacted formaldehyde completely in microcapsules preparation process, human body is damaged.Known according to the principle of in-situ polymerization, the wall material of in-situ polymerization forms by sedimentation, so the unavoidable coarse injustice of surface of microcapsule.
In sum, the existing technology that is applied to material self-healing is mainly situ aggregation method, the microcapsules that are wherein applied in coating have the one-step method of employing to prepare Lauxite parcel semi-drying, the microcapsules of drying oil, also there is the melamine-formaldehyde resin of employing parcel semi-drying, the microcapsules of drying oil, but said method main raw material(s) comprises harmful formaldehyde, formaldehyde likely reacts incomplete and residual human body is damaged, and this technique length consuming time, the common fault of in-situ polymerization is the coarse injustice of surface of microcapsule, microcapsules prepared by this technique add in coating can produce stronger light scattering, paint film is caused to more negative effect.
Summary of the invention
In order to overcome the defect of prior art, the invention provides a kind of preparation method of the microcapsules that are applied to the coated self-drying type film forming matter in coating.Application interface polymerization parcel core-clad material matter of the present invention is that self-drying type film forming matter (comprising as long oil alkyd resin, thermoplastic acrylic resin, semi-drying oil and dryness wet goods) is prepared microcapsules.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
A preparation method for the microcapsules of coated self-drying type film forming matter, comprises the following steps:
A) auxiliary agent and water are mixed, prepare the aqueous solution of auxiliary agent;
B) mix by capsule-core material with for the preparation of the reaction monomers of cyst wall;
C) mixture described step b) being obtained add adjuvant water solution a) in, mechanical dispersion forms stable dispersion liquid;
D) add amine substance, on interface, react, form microcapsules;
E) microcapsules that prepare are filtered, wash, are dried.
The present invention provides a kind of microcapsules in conjunction with capsule technique, for the self-healing of paint film, extends the guard time of paint film, reaches save trouble and labor saving of labor's object.In the preparation method who is applied to self-drying type film forming matter microcapsules in coating provided by the invention, self-drying type film forming matter is wrapped in polymer as core, and these microcapsules can be used in reparation and the anticorrosion of paint film.Microcapsules are added in coating, and microcapsules can stably exist in paint film; In the time that paint film is impaired, the microcapsules of damaged part are torn, and automatically discharge renovation agent (self-drying type film forming matter), and under natural environment, self-drying type film forming matter dry solidification, repairs paint film damaged part, extend paint film service life.
Preparation in accordance with the present invention, described adition process is carried out lentamente.
Preparation in accordance with the present invention, in the aqueous solution of the auxiliary agent that step a) is prepared, contain auxiliary agent 0.1wt%-5wt%, be for example 0.3wt%, 0.8wt%, 1.5wt%, 2.3wt%, 3.4wt%, 4.0wt%, 4.7wt% etc., be preferably 0.2wt%-4.5wt%, more preferably 0.3wt%-4wt%.
Preferably, described auxiliary agent is one or more the mixing in anionic emulsifier, nonionic emulsifier and polymer electrolyte emulsifying agent.
Anionic emulsifier can comprise that sulfate, sulfonate and phosphate etc. commonly use commercially available product; Nonionic emulsifier can comprise the conventional commercially available prod such as ethers, ester class; High score subclass emulsifying agent can comprise natural polymer emulsifying agent and synthetic polymer electrolyte emulsifying agent.
Preparation in accordance with the present invention, step b) described capsule-core material is self-drying type film forming matter, is preferably drying oil if tung oil, linseed oil, semi-drying oil are as one or more the mixing in soybean oil, long oil alkyd resin, thermoplastic acrylic resin.The source that the present invention is self-drying type film forming matter to described capsule-core material does not have special restriction, drying oil, semi-drying oil all can, adopt commercial goods well known to those skilled in the art, while using drying oil or semi-drying oil as capsule-core material, drying oil or semi-drying oil comprise terres rares drier, as the product better effects if making while using the terres rares drier below 5/10000ths.Long oil alkyd resin, thermoplastic acrylic resin are also commercially available prod well known to those skilled in the art, as adopted long oil alkyd resin 974, the thermoplastic acrylic resin 6651 etc. of large prosperous resin (Huizhou) Co., Ltd.
Preparation in accordance with the present invention, step b) described reaction monomers is the material that contains activity-NCO group, is preferably isocyanates material.
The mixing of one or more in the material that addition product that preferably, described isocyanates material can be isocyanates monomer, isocyanates base polymer and isocyanates and alcohol etc. contains activity-NCO group.
Preparation in accordance with the present invention, step b) described capsule-core material and the mass ratio of reaction monomers is 0.1-10:1, for example, be 0.4:1,1.2:1,2.0:1,4.0:1,7.0:1,9.5:1 etc., is preferably 0.5-9:1, more preferably 1-8:1.
Preparation in accordance with the present invention, the step c) mass ratio of described mixture and adjuvant water solution is 0.05-0.5:1, for example, be 0.09:1,0.13:1,0.20:1,0.34:1,0.47:1 etc.
Preparation in accordance with the present invention, steps d) described amine substance is one or more the mixing in polyamine, described amine substance is the another kind of reaction monomers as wall material.
Preferably, described polyamine is one or more the mixing in polyamine monomer, polymerization polyamine.
Preferably, the amine substance adding and the mass ratio of reaction monomers are 0.01-1:1, for example, be 0.03:1,0.08:1,0.15:1,0.34:1,0.50:1,0.70:1,0.85:1,0.97:1 etc., are preferably 0.05-1:1, more preferably 0.1-1:1.
Preferably, the temperature of described reaction is room temperature, is preferably 15-35 DEG C, for example, be 18 DEG C, 22 DEG C, 27 DEG C, 31 DEG C, 34 DEG C etc.
Preferably, the time of described reaction is more than 2h, to be preferably 3-10h.
As optimal technical scheme, preparation method of the present invention, comprises the following steps:
A) auxiliary agent and water are mixed, preparation is containing the aqueous solution of the auxiliary agent of auxiliary agent 0.1wt%-5wt%;
B) mix by capsule-core material with for the preparation of the reaction monomers of cyst wall material; Described capsule-core material and the mass ratio of reaction monomers are 0.1-10:1;
C) mixture described step b) being obtained add adjuvant water solution a) in, mechanical dispersion forms stable dispersion liquid; The mass ratio of described mixture and adjuvant water solution is 0.05-0.5:1;
D) add amine substance, under room temperature, on interface, react more than 2h, form microcapsules; The mass ratio of the polyamine adding and cyst wall material is 0.01-1:1;
E) microcapsules that prepare are filtered, wash, are dried.
The microcapsules filtration for preparing, washing, dry process, those skilled in the art can select according to prior art, wash then air drying such as the present invention makes water or suitable organic solvent after can filtering as ethanol, acetone etc.
Microcapsules provided by the invention can be used in commercially available most of coating, for extending the paint film life-span, as: solvent-borne type or water-borne acrylic resin, alkyd resins, polyurethane and epoxy resin coating etc., that is to say coating type do not had to special restriction.The mass ratio of coating and microcapsules is preferably 8-15:1-4, more preferably 8-9:1-2; The microcapsules that prepare are added in the coating having prepared, be uniformly dispersed and get final product application.Capsule-core material gets final product dry solidification under field conditions (factors), repairs the impaired part of paint film, reaches the effect of self-healing, extends the service life of paint film, extends the guard time to ground.
Being explained as follows of relational language in literary composition:
Self-healing technology: be the characteristic of mimic biology structure, realize material and realize the oneself healing of material under the condition that there is no external condition or have the external condition of little easy realization to participate in.
In-situ polymerization: the prepolymer of the coating material of this technique dissolves in continuous phase, capsule-core is dispersed in continuous phase, polymerisation occurs in core surface, along with the carrying out of polymerisation, performed polymer is insoluble to continuous phase gradually, be deposited on capsule-core surface, due to constantly carrying out of crosslinked and polymerisation, finally form the microcapsule shell of capsule-core material.
Interfacial polymerization: by the common emulsification of monomer A of core and wall material reaction use or be dispersed in one and be dissolved with wall material with in the continuous phase of monomers B, then monomer A, B form the technique of microcapsules on core surface through polymerisation.
The present invention adopts isocyanates and amine interfacial polymerization to prepare microcapsules, utilizes the fast reaction of isocyano and amido to prepare microcapsules.Preparation method of the present invention needs heating hardly, thereby has saved the energy, and energy consumption is low, and technique is simple, easy to operate.And because interface polymerization reaction is the reaction occurring on oil-water interfaces, and form wall material unlike in-situ polymerization by sedimentation, thereby surface of microcapsule is relatively smooth.Be applied to realize in coating the self-healing of damage, extend the service life of coating.
And microcapsules prepared by the present invention can directly add in coating, in the time that paint film is impaired, can cause the microcapsules rupture in paint film, thereby discharge core material, the capsule-core material discharging infiltrates into damaged part along gap under siphonic effect effect, capsule-core material dry solidification under field conditions (factors), repair the impaired part of paint film, reach the effect of self-healing, thereby extend the guard time of paint film to ground, extend the service life of paint film, reach and reduce the object of repairing number of times, thereby artificial and cost are saved, also reduced because repairing the work causing and stagnated the wasting of resources bringing simultaneously.
Brief description of the drawings
Fig. 1 is the microscope enlarged diagram of the microcapsules prepared of the embodiment of the present invention 1;
Fig. 2 is that microcapsules prepared by embodiment 1 are distributed to the microscope schematic diagram in common water paint;
Fig. 3 is the photo after model immersion 10d; Left: to use and do not add the coating of microcapsules for the model of coating, the right side: the model that the coating that uses the microcapsules that add embodiment 1 is coating.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only, for helping to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1:
1) 1g nonionic emulsifier Tween80 is dissolved in 100g water, and is placed in the four-hole boiling flask of 500ml;
2) by 30g tung oil (comprise ten thousand/ terres rares drier) and 10g WANNATE MDI-50 (methyl diphenylene diisocyanate, WANNATE MDI-50 is 2, the mixture of 4'-methyl diphenylene diisocyanate and 4,4'-methyl diphenylene diisocyanate) mix;
3) by mix 2) add 1) in, high-speed stirred, forms stable dispersion liquid;
4) 3g diethylenetriamine is slowly added in dispersion liquid, 25 DEG C of reaction temperatures, reaction 5h, forms microcapsules;
5) microcapsules that prepare are filtered, washed and are dried.
The microscope scanned picture of microcapsules prepared by this embodiment is shown in Fig. 1.As can be seen from the figure, the Microcapsules Size of preparation is nearly all below 50 microns, and surface is more smooth, can more easily add in coating.
Join paint, application and paint film property inspection experiment:
The present invention compares test with commercially available water paint, and microcapsules prepared by embodiment 1 add in water paint, and the mass ratio of water paint and microcapsules is 9:1, mixes then masking, test decay resistance after maintenance is dry.
Microcapsules are distributed to the microscope schematic diagram in common water paint by Fig. 2, and microcapsules can be distributed in water paint preferably as can be seen from this figure.
Fig. 3 be blank sample and the model immersion 10d that adds microcapsules (my god) after photo; from picture, can find out; the resistance to deionized water corrosivity of paint film that adds microcapsules is better than blank plate; in this explanation paint film, add after microcapsules; in the time that paint film sustains damage; the microcapsules of damage location are torn simultaneously, discharge capsule-core material and repair damaged part, extend the guard time of paint film to ground.
Embodiment 2:
1) 1g nonionic emulsifier Tween80 is dissolved in 100g water, and is placed in the four-hole boiling flask of 500ml;
2) by 30g long oil alkyd resin (long oil alkyd resin 974 of large prosperous resin (Huizhou) Co., Ltd) and 10g WANNATE MDI-50 (methyl diphenylene diisocyanate, WANNATE MDI-50 is 2, the mixture of 4'-methyl diphenylene diisocyanate and 4,4'-methyl diphenylene diisocyanate) mix;
3) by mix 2) add 1) in, high-speed stirred, forms stable dispersion liquid;
4) 3g diethylenetriamine is slowly added in dispersion liquid, 25 DEG C of reaction temperatures, reaction 5h, forms microcapsules;
5) microcapsules that prepare are filtered, washed and are dried.
Embodiment 3:
1) 1g nonionic emulsifier Tween80 is dissolved in 100g water, and is placed in the four-hole boiling flask of 500ml;
2) by 30g thermoplastic acrylic resin (large prosperous resin (Huizhou) Co., Ltd 6651) and 10g WANNATE MDI-50 (methyl diphenylene diisocyanate, WANNATE MDI-50 is 2, the mixture of 4'-methyl diphenylene diisocyanate and 4,4'-methyl diphenylene diisocyanate) mix;
3) by mix 2) add 1) in, high-speed stirred, forms stable dispersion liquid;
4) 3g diethylenetriamine is slowly added in dispersion liquid, 25 DEG C of reaction temperatures, reaction 5h, forms microcapsules;
5) microcapsules that prepare are filtered, washed and are dried.
Embodiment 4:
1) 0.5g anionic emulsifier dodecyl sodium sulfate is dissolved in 100g water, and is placed in the four-hole boiling flask of 500ml;
2) 5g soybean oil (comprise ten thousand/ terres rares drier) and 10gN3390 (Bayer, hexamethylene diisocyanate trimer) are mixed;
3) by mix 2) add 1) in, high-speed stirred, forms stable dispersion liquid;
4) 5g diethylenetriamine is slowly added in dispersion liquid, 20 DEG C of reaction temperatures, reaction 10h, forms microcapsules;
5) microcapsules that prepare are filtered, washed and are dried.
Embodiment 5:
1) 0.5g nonionic emulsifier Tween80 and 0.5g anionic emulsifier dodecyl sodium sulfate are dissolved in 100g water, and are placed in the four-hole boiling flask of 500ml;
2) 10g linseed oil (comprise ten thousand/ terres rares drier) and 1g IPDI (IPDI) are mixed;
3) by mix 2) add 1) in, high-speed stirred, forms stable dispersion liquid;
4) 0.2g diethylenetriamine is slowly added in dispersion liquid, 30 DEG C of reaction temperatures, reaction 2h, forms microcapsules;
5) microcapsules that prepare are filtered, washed and are dried.
Microcapsules prepared by embodiment 1-5 add in water paint, and addition is 10%, and making sheet under the same terms scratches after maintenance is dry, and immersion, observes corrosion condition as table 1.
For the water-fast corrosivity of convenient statement paint film, divide rank by following standard:
0 grade: do not occur corrosion;
1 grade: have the cut appearance corrosion that is less than 1/10th;
2 grades: have the cut appearance corrosion that is less than 1/5th;
3 grades: have the cut appearance corrosion that is less than 1/2nd;
4 grades: all corrosion appears in cut.
Table 1
| Sample | Immersion 3d | Immersion 5d | Immersion 7d | Immersion 10d | Immersion 30d |
| Blank | 3 | 4 | 4 | 4 | 4 |
| Embodiment 1 | 0 | 0 | 1 | 1 | 1 |
| Embodiment 2 | 0 | 0 | 0 | 0 | 1 |
| Embodiment 3 | 0 | 0 | 0 | 0 | 1 |
| Embodiment 4 | 0 | 1 | 1 | 2 | 3 |
| Embodiment 5 | 0 | 0 | 1 | 1 | 2 |
As can be seen from Table 1, use the microcapsules prepared of the present invention to add to carry out coating in coating and carry out coating than the coating of the microcapsules that do not add the present invention to prepare, in service life that can significant prolongation paint film, extend the guard time to ground.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for the microcapsules of coated self-drying type film forming matter, comprises the following steps:
A) auxiliary agent and water are mixed, prepare the aqueous solution of auxiliary agent;
B) mix by capsule-core material with for the preparation of the reaction monomers of cyst wall material;
C) mixture described step b) being obtained add adjuvant water solution a) in, mechanical dispersion forms stable dispersion liquid;
D) add amine substance, on interface, react, form microcapsules;
E) microcapsules that prepare are filtered, wash, are dried.
2. preparation method according to claim 1, is characterized in that, described adition process is carried out lentamente.
3. preparation method according to claim 1 and 2, is characterized in that, in the aqueous solution of the auxiliary agent that step a) is prepared, containing auxiliary agent 0.1wt%-5wt%, is preferably 0.2wt%-4.5wt%, more preferably 0.3wt%-4wt%;
Preferably, described auxiliary agent is one or more the mixing in anionic emulsifier, nonionic emulsifier and polymer electrolyte emulsifying agent.
4. according to the preparation method described in claim 1-3 any one, it is characterized in that, step b) described capsule-core material is self-drying type film forming matter, is preferably one or more the mixing in drying oil, semi-drying oil, long oil alkyd resin, thermoplastic acrylic resin;
Preferably, described reaction monomers is the material that contains activity-NCO group, is preferably isocyanates material;
Preferably, described isocyanates material is one or more the mixing in the addition product of isocyanates monomer, isocyanates base polymer, isocyanates and alcohol.
5. according to the preparation method described in claim 1-4 any one, it is characterized in that, step b) described capsule-core material and the mass ratio of reaction monomers is 0.1-10:1, is preferably 0.5-9:1, more preferably 1-8:1.
6. according to the preparation method described in claim 1-5 any one, it is characterized in that, the step c) mass ratio of described mixture and adjuvant water solution is 0.05-0.5:1.
7. according to the preparation method described in claim 1-6 any one, it is characterized in that steps d) described amine substance is one or more the mixing in polyamine.
8. preparation method according to claim 7, is characterized in that, described polyamine is one or more the mixing in polyamine monomer, polymerization polyamine.
9. according to the preparation method described in claim 1-8 any one, it is characterized in that steps d) amine substance adding and the mass ratio of reaction monomers be 0.01-1:1, is preferably 0.05-1:1, more preferably 0.1-1:1;
Preferably, the temperature of described reaction is room temperature, is preferably 15-35 DEG C;
Preferably, the time of described reaction is more than 2h, to be preferably 3-10h.
10. according to the preparation method described in claim 1-9 any one, it is characterized in that, comprise the following steps:
A) auxiliary agent and water are mixed, preparation is containing the aqueous solution of the auxiliary agent of auxiliary agent 0.1wt%-5wt%;
B) mix by capsule-core material with for the preparation of the reaction monomers of cyst wall material; The mass ratio of described capsule-core material and the monomer of cyst wall material is 0.1-10:1;
C) mixture described step b) being obtained add adjuvant water solution a) in, mechanical dispersion forms stable dispersion liquid; The mass ratio of described mixture and adjuvant water solution is 0.05-0.5:1;
D) add amine substance, under room temperature, on interface, react more than 2h, form microcapsules; The mass ratio of the polyamine adding and cyst wall material is 0.01-1:1;
E) microcapsules that prepare are filtered, wash, are dried.
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| CN114316789A (en) * | 2021-12-21 | 2022-04-12 | 东周化学工业（昆山）有限公司 | Self-repairing scratch-resistant wear-resistant ultraviolet curing coating for plastic products and application thereof |
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