CN109852136B - Single-component ink and water-based ink coating for 3C glass - Google Patents
Single-component ink and water-based ink coating for 3C glass Download PDFInfo
- Publication number
- CN109852136B CN109852136B CN201811618201.2A CN201811618201A CN109852136B CN 109852136 B CN109852136 B CN 109852136B CN 201811618201 A CN201811618201 A CN 201811618201A CN 109852136 B CN109852136 B CN 109852136B
- Authority
- CN
- China
- Prior art keywords
- water
- parts
- modified
- ink
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910001868 water Inorganic materials 0.000 title claims abstract description 96
- 239000011521 glass Substances 0.000 title claims abstract description 75
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 16
- 239000000049 pigment Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 87
- 239000005543 nano-size silicon particle Substances 0.000 claims description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 18
- 238000007639 printing Methods 0.000 claims description 18
- 238000007650 screen-printing Methods 0.000 claims description 16
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229920000178 Acrylic resin Polymers 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920005749 polyurethane resin Polymers 0.000 claims description 8
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 229920000180 alkyd Polymers 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical class CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 4
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical class N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims description 4
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical class N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 4
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 4
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical class C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical class O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical class O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 3
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 claims description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- 238000001723 curing Methods 0.000 abstract description 47
- 238000000034 method Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 9
- 238000001029 thermal curing Methods 0.000 abstract description 9
- 230000032683 aging Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 230000008602 contraction Effects 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000000805 composite resin Substances 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 239000000976 ink Substances 0.000 description 105
- 239000000203 mixture Substances 0.000 description 39
- 239000000377 silicon dioxide Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 230000036541 health Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- -1 isocyanic acid radical Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 241000935974 Paralichthys dentatus Species 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a single-component ink and a water-based ink coating for 3C glass, which comprises the following components: the coating comprises, by weight, 25-45 parts of organic-inorganic composite water-based resin, 5-10 parts of pigment, 32-55 parts of filler, 10-25 parts of water, 1-5 parts of closed water-based curing agent and 0.01-1.0 part of auxiliary agent. The single-component ink for 3C glass disclosed by the invention uses the organic-inorganic composite water-based resin, is good in chemical resistance, excellent in ultraviolet light aging resistance, good in adhesion to 3C glass, very high in surface hardness and small in thermal expansion and cold contraction. In the high-temperature curing process, hydroxyl or carboxyl in the organic-inorganic composite resin and the closed water-based curing agent are subjected to a crosslinking reaction to form an interpenetrating network structure, so that the performances of all components are fully exerted, and an ink coating is formed on the surface of the 3C glass. The closed water-based curing agent can also provide reasonable thermal curing speed, and the requirement that the thermal curing time of the ink in the 3C glass industry is short is met.
Description
Technical Field
The invention relates to the field of ink, in particular to single-component ink for 3C glass. In addition, the invention also relates to a water-based ink coating comprising the single-component ink for 3C glass.
Background
The two-component thermosetting solvent type decorative ink commonly used in the industry at present needs a long time for oil blending before use, the service life of the blended ink is short, the oil blending frequency is high, more waste oil ink is generated, more waste oil needs to be treated, the production efficiency is relatively low, the ink loss is large, and the production cost is high. Meanwhile, more waste printing ink is generated, so that subsequent treatment is needed, and secondary pollution is caused to the environment. The carrier in the printing ink uses a large amount of solvent, the discharge amount of VOC is large in the printing ink curing process, the environment is polluted, the ozone layer is damaged, and meanwhile, the volatilization of the solvent causes great damage to the body health of staff. Therefore, an ink is urgently needed, the production efficiency of 3C glass enterprises can be improved, the production cost is reduced, the discharge of VOC is greatly reduced, the environment is protected, the physical health of workers is protected, and the ink is revolutionary change to the 3C glass industry.
Disclosure of Invention
The invention provides a single-component ink and water-based ink coating for 3C glass, which aims to solve the problems that in the prior art, double-component heat-curing solvent-based ink is adopted, the oil mixing process is troublesome, and the service time is short; the discharge amount of VOC is large, the environment is polluted, and the body health of staff is influenced; the waste of the printing ink is serious, which causes the technical problem of high production cost.
The technical scheme adopted by the invention is as follows:
a single-component ink for 3C glass comprises the following components: the coating comprises, by weight, 25-45 parts of organic-inorganic composite water-based resin, 5-10 parts of pigment, 32-55 parts of filler, 10-25 parts of water, 1-5 parts of closed water-based curing agent and 0.01-1.0 part of auxiliary agent.
Further, the composition comprises the following components: 22-43 parts of organic-inorganic composite water-based resin, 5-9 parts of pigment, 32-52 parts of filler, 12-23 parts of water, 1.5-4.5 parts of closed water-based curing agent and 0.01-1.0 part of auxiliary agent.
Further, the composition comprises the following components: the coating comprises, by weight, 28-43 parts of organic-inorganic composite water-based resin, 5-8 parts of pigment, 35-50 parts of filler, 15-23 parts of water, 2-4.4 parts of closed water-based curing agent and 0.01-1.0 part of auxiliary agent.
Further, the organic-inorganic composite water-based resin is C60 and nano silica modified resin.
Further, the C60 and nano-silica modified resin is one or more of C60 and nano-silica modified acrylic resin, C60 and nano-silica modified polyurethane resin, C60 and nano-silica modified alkyd resin, C60 and nano-silica modified silicone resin or C60 and nano-silica modified polyester resin.
Furthermore, the closed water-based curing agent adopts one or more of modified toluene diisocyanate, modified diphenylmethane diisocyanate, modified hexamethylene diisocyanate, modified isophorone diisocyanate, modified dicyclohexylmethane-4, 4' -diisocyanate, modified xylylene diisocyanate, modified tetramethyl m-xylylene diisocyanate, modified methylcyclohexane diisocyanate, modified norbornane diisocyanate or modified 1, 4-phenylene diisocyanate.
Further, the pigment adopts one or more of carbon black, titanium dioxide, quinacridone red, phthalocyanine blue, permanent violet and permanent yellow; and/or the filler is one or more of talcum powder, barium sulfate and calcium carbonate.
Further, deionized water is adopted as water; and/or the auxiliary agent comprises one or more of a leveling agent, a dispersing agent, a defoaming agent or a substrate wetting agent.
According to another aspect of the present invention, there is also provided a method for preparing an aqueous ink coating, comprising the steps of: and (3) screen-printing the single-component ink for 3C glass on a 3C glass substrate, baking at 150-180 ℃, and curing to obtain the water-based ink coating.
Furthermore, the silk screen is 300-350 meshes; the curing time is 15 min-30 min.
The invention has the following beneficial effects:
the single-component ink for 3C glass disclosed by the invention uses the organic-inorganic composite water-based resin, is good in chemical resistance, excellent in ultraviolet light aging resistance, good in adhesion to 3C glass, very high in surface hardness and small in thermal expansion and cold contraction. In the high-temperature curing process, hydroxyl or carboxyl in the organic-inorganic composite resin and the closed water-based curing agent are subjected to a crosslinking reaction to form an interpenetrating network structure, so that the performances of all components are fully exerted, and an ink coating is formed on the surface of the 3C glass. The closed water-based curing agent can also provide reasonable thermal curing speed, so that the ink can meet the requirement of shorter thermal curing time in the 3C glass industry, and the curing time is only 15-30 min.
The single-component ink for 3C glass has good stability at normal temperature, and ensures that the storage time of the ink can meet more than six months. The single-component printing ink for 3C glass is composed of the closed curing agent, the problem of service cycle is avoided in the using process, the printing viscosity is adjusted, only the addition amount of water needs to be changed, and the used printing ink can be recycled. The single-component printing ink for 3C glass improves the construction environment, belongs to a green and environment-friendly product, and is suitable for modern mass production. As the single-component ink for 3C glass completely adopts water as the diluent, the VOC emission is zero during thermocuring, the environment is protected, and the damage of the volatilization of organic solvents to the atmosphere and the ozone layer is avoided. Meanwhile, an organic solvent is not used in the screen printing process, so that the construction environment is greatly improved, the physical health of workers is protected, and the silk screen printing method belongs to a green and environment-friendly product and is suitable for modern mass production.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention is described in further detail below.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
The single-component ink for 3C glass of the embodiment comprises the following components: the coating comprises, by weight, 25-45 parts of organic-inorganic composite water-based resin, 5-10 parts of pigment, 32-55 parts of filler, 10-25 parts of water, 1-5 parts of closed water-based curing agent and 0.01-1.0 part of auxiliary agent. The single-component ink for 3C glass disclosed by the invention uses the organic-inorganic composite water-based resin, is good in chemical resistance, excellent in ultraviolet light aging resistance, good in adhesion to 3C glass, very high in surface hardness and small in thermal expansion and cold contraction. In the high-temperature curing process, hydroxyl or carboxyl in the organic-inorganic composite resin and the closed water-based curing agent are subjected to a crosslinking reaction to form an interpenetrating network structure, so that the performances of all components are fully exerted, and an ink coating is formed on the surface of the 3C glass. The closed water-based curing agent can also provide reasonable thermal curing speed, so that the ink can meet the requirement of shorter thermal curing time in the 3C glass industry, and the curing time is only 15-30 min.
The single-component printing ink for the 3C glass has good stability at normal temperature, and the storage time of the printing ink can be ensured to meet more than six months. The single-component printing ink for 3C glass is composed of the closed curing agent, the problem of service cycle is avoided in the using process, the printing viscosity is adjusted, only the addition amount of water needs to be changed, and the used printing ink can be recycled. The single-component printing ink for 3C glass improves the construction environment, belongs to a green and environment-friendly product, and is suitable for modern mass production. As the single-component ink for 3C glass completely adopts water as the diluent, the VOC emission is zero during thermocuring, the environment is protected, and the damage of the volatilization of organic solvents to the atmosphere and the ozone layer is avoided. Meanwhile, an organic solvent is not used in the screen printing process, so that the construction environment is greatly improved, the physical health of workers is protected, and the silk screen printing method belongs to a green and environment-friendly product and is suitable for modern mass production.
In the embodiment, the paint comprises the following components: 22-43 parts of organic-inorganic composite water-based resin, 5-9 parts of pigment, 32-52 parts of filler, 12-23 parts of water, 1.5-4.5 parts of closed water-based curing agent and 0.01-1.0 part of auxiliary agent.
In the embodiment, the paint comprises the following components: the coating comprises, by weight, 28-43 parts of organic-inorganic composite water-based resin, 5-8 parts of pigment, 35-50 parts of filler, 15-23 parts of water, 2-4.4 parts of closed water-based curing agent and 0.01-1.0 part of auxiliary agent.
In this example, the organic-inorganic composite aqueous resin was C60 and a nano silica modified resin. The C60 molecular layer has good flexibility, good adhesive force on common materials such as glass, ceramics, metal and the like, high strength, strong ultraviolet aging resistance and small coefficient of expansion with heat and contraction with cold, but the C60 is difficult to react and is not dissolved with water and alcohol solvents, but can be well dissolved in the water and alcohol solvents after being grafted with hydroxyl on the surface. The water solubility of the C60 is improved by hydroxylation reaction, the effect of completely dissolving the C60 in water is achieved, hydroxyl groups on the surfaces of hydroxylated C60 and nano silicon dioxide form hydrogen bonds with polar groups in resin, and the resin can coat C60 and nano silicon dioxide to obtain modified resin, namely C60 and nano silicon dioxide modified resin.
The particle size of the nano silicon dioxide ranges from 1nm to 100nm, and the microstructure is spherical and is in a flocculent and reticular particle structure. The nano silicon dioxide is processed into the nano silicon dioxide transparent liquid, so that the application range of the nano silicon dioxide is greatly improved, the nano silicon dioxide transparent liquid can be made into a transparent silicon oxide glass film coating material, and the nano silicon dioxide transparent liquid can be mixed with various water-based resins, has high transparency, improves the hardness and the friction resistance of the resins, improves the adhesive force of the resins to glass, improves the ultraviolet aging resistance of the resins, and reduces the expansion and contraction degree of the resins. The organic-inorganic composite water-based resin is used as a film forming substance during thermocuring, has higher curing speed, can reduce oil mixing procedures to improve the production efficiency, and simultaneously uses water as a solvent to avoid discharge of VOC, thereby protecting the environment and the physical health of personnel.
The synthesis method of the C60 and nano silicon dioxide modified resin comprises the following steps: (1) mixing hydroxylated C60 with hydrophilic nano-silica, adding n-butyl alcohol, stirring, heating, slowly adding a silane coupling agent, reacting for 3-3.5 hours under heat preservation, vacuumizing, and separating n-butyl alcohol to obtain a mixture a of C60 and the nano-silica, wherein epoxy groups are carried on the surface of the mixture a; (2) and (3) adding the aqueous resin into the mixture a, stirring, heating, reacting, and cooling to obtain the C60 and nano silica modified resin. In the step (1), the adding amount mass ratio of the hydroxylated C60 to the hydrophilic nano-silica is 1-1.5: 9, the heating temperature is 60-70 ℃, the adding amount of n-butanol is 2-3 times of the total mass of the hydroxylated C60 and the hydrophilic nano-silica, and the silane coupling agent is 10% of the total mass of the hydroxylated C60 and the hydrophilic nano-silica; in the step (2), the mixture a and the water-soluble resin are added in a mass ratio of 1-2: 20, the heating temperature is 50-60 ℃, and the reaction lasts for 1-2 hours. The water-based resin is one of acrylic resin, polyurethane resin, alkyd resin, organic silicon resin or polyester resin.
Preferably, the C60 and nano-silica modified resin is one or more of C60 and nano-silica modified acrylic resin, C60 and nano-silica modified polyurethane resin, C60 and nano-silica modified alkyd resin, C60 and nano-silica modified silicone resin or C60 and nano-silica modified polyester resin. The resin modification can improve the strength of the resin, but can also reduce the toughness of the resin, and the improvement of the toughness can lead to insufficient strength, so that the introduction of the nano silica particles can simultaneously improve the two defects. The hydroxylated C60 has high strength, good toughness and flexibility, and the nano silicon dioxide is superfine nano, so that the nano silicon dioxide has a plurality of unique properties, such as optical performance of resisting ultraviolet rays, and the ageing resistance, strength and chemical resistance of other materials can be improved. And the surface of the nano silicon dioxide is rich in hydroxyl, and forms hydrogen bonds with polar groups in resin, so that the crosslinking reaction with the closed water-based curing agent is accelerated. The resin modified by hydroxylated C60 and nano silicon dioxide has the advantages of mechanical strength, toughness, ultraviolet aging resistance and chemical resistance which are greatly improved after being cured.
In this embodiment, the blocked aqueous curing agent is one or more of modified Toluene Diisocyanate (TDI), modified diphenylmethane diisocyanate (MDI), modified Hexamethylene Diisocyanate (HDI), modified isophorone diisocyanate (IPDI), modified dicyclohexylmethane-4, 4' -diisocyanate (HMDI), modified Xylylene Diisocyanate (XDI), modified tetramethylm-xylylene diisocyanate (TMXDI), modified methylcyclohexane diisocyanate (HTDI), modified norbornane diisocyanate (NBDI) or modified 1, 4-xylylene diisocyanate (PPDI). The closed water-based curing agent has the advantages that the isocyanic acid radical with higher activity is closed at normal temperature, the activity is recovered at the temperature of over 150 ℃, and the isocyanic acid radical reacts with hydroxylated C60 in the organic-inorganic composite resin, nano silicon dioxide and hydroxyl and carboxyl on the surface of the resin to form an interpenetrating network structure, the performances of all components are fully exerted, and an ink coating meeting the performance requirements of the 3C industry is formed on the surface of glass.
Preferably, the blocked waterborne curing agent adopts one or more of modified Hexamethylene Diisocyanate (HDI), modified isophorone diisocyanate (IPDI), modified dicyclohexylmethane-4, 4' -diisocyanate (HMDI), modified methylcyclohexane diisocyanate (HTDI) or modified norbornane diisocyanate (NBDI).
In this embodiment, the pigment is one or more of carbon black, titanium dioxide, quinacridone red, phthalocyanine blue, permanent violet, and permanent yellow. And/or the filler is one or more of talcum powder, barium sulfate and calcium carbonate. The pigment provides various colors for the single-component printing ink for 3C glass, and meets the requirements of different crowds. The appropriate filler provides appropriate thixotropy for the single-component ink composition for the 3C glass, oil seepage during printing is prevented, meanwhile, the characteristic of low expansion with heat and contraction with cold is provided for the single-component ink composition for the 3C glass, fine patterns can be printed by using a 300-350-mesh silk screen for the single-component ink for the 3C glass through selecting the appropriate filler and matching a thermosetting system by adjusting the pressure, the angle and the like of a scraper, and the water-based ink coating with good adhesion to the 3C glass can be obtained in an oven at the temperature of 150-180 ℃.
In this embodiment, deionized water is used as water. And/or the auxiliary agent comprises one or more of a leveling agent, a dispersing agent, a defoaming agent or a substrate wetting agent.
The preparation method of the single-component ink for 3C glass comprises the following steps: sequentially adding the organic-inorganic composite water-based resin, the closed water-based curing agent, the water, the pigment, the filler and the auxiliary agent while stirring at the stirring speed of 800-1500 revolutions per minute, uniformly mixing, dispersing for 15-30 min at the rotating speed of 2000-3000 revolutions per minute, and grinding on a sand mill until the granularity is less than 5 mu m to obtain the single-component printing ink for 3C glass.
According to another aspect of the present invention, there is also provided a method for preparing an aqueous ink coating, comprising the steps of: and (3) screen-printing the single-component ink for 3C glass on a 3C glass substrate, baking at 150-180 ℃, and curing to obtain the water-based ink coating. The preparation method of the water-based ink coating is simple to operate, the water-based ink coating is obtained by baking and UV curing after the water-based ink coating is printed on a 3C glass substrate, the curing is fast, the yield is high, the cost is low, and the preparation method is suitable for mass production.
The blocked water-based curing agent for the 3C glass single-component ink has high activity of isocyanic acid radical blocking at normal temperature, can recover activity only when the temperature exceeds 150 ℃, and can react with organic-inorganic composite resin to generate crosslinking reaction, so that the baking temperature is 150-180 ℃, the crosslinking reaction is facilitated, and the 3C glass single-component ink can form a water-based ink coating with good adhesive force on a 3C glass substrate.
In this embodiment, the mesh is 300-350 mesh. The curing time is 15 min-30 min. The obtained 300-350-mesh silk screen for the single-component ink for the 3C glass can be printed to obtain a fine pattern by adjusting the pressure, the angle and the like of a scraper, and the water-based ink coating with good adhesion to the 3C glass can be obtained by curing for 15-30 min in an oven at the temperature of 150-180 ℃, so that the requirement of the industry on high curing speed is met. The silk screen is used for 300-350-mesh silk screen printing, so that the water-based ink coating is uniformly distributed and is tightly combined with the 3C glass substrate. The curing time is obviously shortened by using the closed water-based curing agent, and the water-based ink coating meeting the performance requirements of the 3C industry can be realized by curing for 15-30 min.
Examples
The synthesis method of the C60 and nano silicon dioxide modified resin comprises the following steps:
adding 10g of hydroxylated C60 and 80g of hydrophilic nano-silica into a 500ml four-mouth bottle, uniformly mixing, adding 200g of n-butyl alcohol, uniformly stirring and dispersing, heating in a water bath, controlling the temperature to be 70 ℃, dropwise adding (controlling the reaction speed and avoiding over-temperature) 10g of silane coupling agent KH560, reacting for 3 hours under heat preservation, vacuumizing, and separating the n-butyl alcohol to obtain a mixture a of C60 and the nano-silica, wherein the surface of the mixture a is provided with an epoxy group;
adding 15g of the mixture a into a 500ml three-necked bottle, adding 200g of water-based resin, uniformly stirring, controlling the temperature of a water bath at 55 ℃, reacting for 1 hour, and cooling to obtain C60 and nano silicon dioxide modified resin for later use. The water-based resin is one of acrylic resin, polyurethane resin, alkyd resin, organic silicon resin or polyester resin.
Materials and equipment used in the following examples are commercially available.
Example 1
The preferred embodiment of the present invention provides a one-component ink for 3C glass, the composition of which is shown in table 1.
Table 1 single component ink for 3C glass of example 1
The rotating speed is 1000 r/min, C60 and nano silicon dioxide modified acrylic resin, C60 and nano silicon dioxide modified polyurethane resin, HDI, IPDI, water, carbon black, talcum powder, barium sulfate, calcium carbonate and auxiliary agent are sequentially added while stirring, the mixture is uniformly mixed, then the mixture is dispersed for 18min at the rotating speed of 3000 r/min, and the mixture is ground on a three-roller machine until the fineness is less than 5 mu m, so that the single-component ink for 3C glass is obtained.
And taking 20g of ground single-component ink for 3C glass, performing 350-mesh screen printing, and curing in an oven at the constant temperature of 180 ℃ for 20min to obtain the water-based ink coating.
Example 2
The preferred embodiment of the present invention provides a one-component ink for 3C glass, the composition of which is shown in table 2.
Table 2 single component ink for 3C glass of example 2
The rotating speed is 800 r/min, C60 and nano-silica modified polyester resin, C60 and nano-silica modified alkyd resin, HDI, HMDI, water, phthalocyanine blue, talcum powder, barium sulfate, calcium carbonate and an auxiliary agent are sequentially added while stirring, the mixture is uniformly mixed, then the mixture is dispersed for 25min at the rotating speed of 2500 r/min, and the mixture is ground on a three-roller machine until the fineness is less than 5 mu m, so that the single-component ink for 3C glass is obtained.
And taking 20g of ground single-component ink for 3C glass, performing 300-mesh screen printing, and curing in an oven at 150 ℃ for 30min to obtain the water-based ink coating.
Example 3
The preferred embodiment of the present invention provides a one-component ink for 3C glass, the composition of which is shown in table 3.
Table 3 single component ink for 3C glass of example 3
The rotation speed is 1200 r/min, C60 and nano-silica modified acrylic resin, C60 and nano-silica modified organic silicon resin, HMDI, HTDI, water, titanium dioxide, talcum powder, barium sulfate, calcium carbonate and auxiliary agent are sequentially added while stirring, the mixture is uniformly mixed, then the mixture is dispersed for 30min at the rotation speed of 2000 r/min, and the mixture is ground on a three-roller machine until the fineness is less than 5 mu m, so that the single-component ink for 3C glass is obtained.
And taking 20g of ground single-component ink for 3C glass, performing 300-mesh screen printing, and curing in an oven at 180 ℃ for 15min to obtain the water-based ink coating.
Example 4
The preferred embodiment of the present invention provides a one-component ink for 3C glass, the composition of which is shown in table 4.
Table 4 single component ink for 3C glass of example 4
The rotation speed is 1200 r/min, C60 and nano silica modified acrylic resin, C60 and nano silica modified polyester resin, HDI, NBDI, water, quinacridone red, talcum powder, barium sulfate, calcium carbonate and auxiliary agent are sequentially added while stirring, the mixture is uniformly mixed, then the mixture is dispersed for 20min at the rotation speed of 3000 r/min, and the mixture is ground to the fineness of less than 5 microns on a three-roller machine, so that the single-component ink for 3C glass is obtained.
And taking 20g of ground single-component ink for 3C glass, performing 300-mesh screen printing, and curing in an oven at 160 ℃ for 20min to obtain the water-based ink coating.
Comparative example 1
Comparative example 1 provides an ink having the composition shown in table 5.
TABLE 5 inks of comparative example 1
The rotating speed is 1200 r/min, the materials of the component A are sequentially added while stirring, after uniform mixing, the materials are dispersed for 20min at the rotating speed of 3000 r/min, and the mixture is ground on a three-roller machine until the fineness is less than 5 mu m, so that the component A is obtained.
And (3) taking 20g of the ground component A, adding 2g of the component B, uniformly stirring, performing screen printing by using a 300-mesh screen, and curing in an oven at the temperature of 160 ℃ for 20min to obtain the ink coating.
Comparative example 2
Comparative example 2 provides an ink having the composition shown in table 6.
TABLE 6 ink of comparative example 2
The rotating speed is 1200 r/min, the materials of the component A are sequentially added while stirring, after uniform mixing, the materials are dispersed for 20min at the rotating speed of 3000 r/min, and the mixture is ground on a three-roller machine until the fineness is less than 5 mu m, so that the component A is obtained.
And (3) taking 20g of the ground component A, adding 2g of the component B, uniformly stirring, performing screen printing by using a 300-mesh screen, and curing in an oven at the temperature of 160 ℃ for 20min to obtain the ink coating.
Comparative example 3
Comparative example 3 provides a one-component ink having the composition shown in table 7.
TABLE 7 Single component ink of comparative example 3
The rotation speed is 1000 revolutions per minute, the nano-silica modified acrylic resin, the nano-silica modified polyurethane resin, HDI, IPDI, water, carbon black, talcum powder, barium sulfate, calcium carbonate and an auxiliary agent are sequentially added while stirring, the mixture is uniformly mixed, then the mixture is dispersed for 18 minutes at the rotation speed of 3000 revolutions per minute, and the mixture is ground on a three-roller machine until the fineness is less than 5 microns, so that the single-component ink is obtained.
And (3) taking 20g of ground single-component ink, performing screen printing by using 350-mesh screen, and curing in an oven at the constant temperature of 180 ℃ for 20min to obtain the ink coating.
Comparative example 4
Comparative example 4 provides a one-component ink whose composition is shown in table 8.
TABLE 8 Single component ink of comparative example 4
The rotation speed is 1000 r/min, C60 and nano silica modified acrylic resin, C60 and nano silica modified polyurethane resin, water, carbon black, talcum powder, barium sulfate, calcium carbonate and auxiliary agent are sequentially added while stirring, the mixture is uniformly mixed, then the mixture is dispersed for 18min at the rotation speed of 3000 r/min, and the mixture is ground on a three-roller machine until the fineness is less than 5 mu m, so that the single-component ink is obtained.
And (3) taking 20g of ground single-component ink, performing screen printing by using 350-mesh screen, and curing in an oven at the constant temperature of 180 ℃ for 50min to obtain the ink coating.
The results of the performance tests of the single-component inks for 3C glass of examples 1-4, the inks of comparative examples 1-2, and the single-component inks of comparative examples 3-4 are set forth in Table 9. The pencil hardness test standard refers to GB/T6739-2006; the adhesion test standard refers to GB/T1720-; the VOC content test standard refers to GB/T23985-2009; testing an arcotesat dyne pen for a dyne value; insulation resistance test FLUKE 1508 resistance tester
Table 9 results of performance testing
As can be seen from Table 7, the single-component ink for 3C glass in example 4 gave the most excellent aqueous ink coating, and the single-component ink for 3C glass prepared according to the present invention gave the most excellent properties as compared with the results obtained in the comparative example.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The single-component printing ink for 3C glass is characterized by comprising the following components: based on the weight portion, the weight ratio of the components,
25-45 parts of organic-inorganic composite water-based resin, 5-10 parts of pigment, 32-55 parts of filler, 10-25 parts of water, 1-5 parts of closed water-based curing agent and 0.01-1.0 part of auxiliary agent;
the organic-inorganic composite water-based resin is C60 and nano silicon dioxide modified resin, and is one or more of C60 and nano silicon dioxide modified acrylic resin, C60 and nano silicon dioxide modified polyurethane resin, C60 and nano silicon dioxide modified alkyd resin, C60 and nano silicon dioxide modified organic silicon resin or C60 and nano silicon dioxide modified polyester resin;
the closed water-based curing agent is one or more of modified toluene diisocyanate, modified diphenylmethane diisocyanate, modified hexamethylene diisocyanate, modified isophorone diisocyanate, modified dicyclohexylmethane-4, 4' -diisocyanate, modified xylylene diisocyanate, modified tetramethyl m-xylylene diisocyanate, modified methylcyclohexane diisocyanate, modified norbornane diisocyanate or modified 1, 4-phenylene diisocyanate;
the pigment adopts one or more of carbon black, titanium dioxide, quinacridone red, phthalocyanine blue, permanent violet and permanent yellow;
the filler is one or more of talcum powder, barium sulfate and calcium carbonate;
the water is deionized water;
the auxiliary agent comprises one or more of a leveling agent, a dispersing agent, a defoaming agent or a substrate wetting agent.
2. The one-component ink for 3C glass according to claim 1, characterized by consisting of the following components: based on the weight portion, the weight ratio of the components,
22-43 parts of organic-inorganic composite water-based resin, 5-9 parts of pigment, 32-52 parts of filler, 12-23 parts of water, 1.5-4.5 parts of closed water-based curing agent and 0.01-1.0 part of auxiliary agent.
3. The one-component ink for 3C glass according to claim 1, characterized by consisting of the following components: based on the weight portion, the weight ratio of the components,
28-43 parts of organic-inorganic composite water-based resin, 5-8 parts of pigment, 35-50 parts of filler, 15-23 parts of water, 2-4.4 parts of closed water-based curing agent and 0.01-1.0 part of auxiliary agent.
4. The preparation method of the water-based ink coating is characterized by comprising the following steps of:
the single-component ink for 3C glass, disclosed by any one of claims 1 to 3, is applied to a 3C glass substrate by screen printing, baked at 150-180 ℃, and cured to obtain a water-based ink coating.
5. The method for producing an aqueous ink coating according to claim 4,
the mesh is 300-350 meshes;
the curing time is 15 min-30 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811618201.2A CN109852136B (en) | 2018-12-28 | 2018-12-28 | Single-component ink and water-based ink coating for 3C glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811618201.2A CN109852136B (en) | 2018-12-28 | 2018-12-28 | Single-component ink and water-based ink coating for 3C glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109852136A CN109852136A (en) | 2019-06-07 |
| CN109852136B true CN109852136B (en) | 2021-12-21 |
Family
ID=66892881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811618201.2A Active CN109852136B (en) | 2018-12-28 | 2018-12-28 | Single-component ink and water-based ink coating for 3C glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109852136B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551417A (en) * | 2019-09-12 | 2019-12-10 | 南雄市星辉化工新材料有限公司 | preparation method and application of air-drying water-based alkyd ink |
| CN110757975A (en) * | 2019-11-07 | 2020-02-07 | 洪泽双友玻璃制品有限公司 | Printing process not easy to wipe for glass products |
| CN114316675B (en) * | 2022-01-21 | 2023-08-04 | 东莞市蓝邦电子五金材料有限公司 | Water-based protective ink and construction process |
| CN115627083B (en) * | 2022-11-09 | 2023-11-10 | 广西民泰纳米科技有限公司 | Preparation method of nano calcium carbonate for asphalt system |
| WO2024127095A1 (en) * | 2022-12-17 | 2024-06-20 | Fujifilm Sericol India Pvt. Ltd. | Screen printing ink composition and a process for its preparation |
| CN115746624A (en) * | 2022-12-31 | 2023-03-07 | 惠州市韵点新材料科技股份有限公司 | Ultrahigh-reflection water-based ink for photovoltaic glass and preparation method thereof |
| CN116891651A (en) * | 2023-06-19 | 2023-10-17 | 深圳市东方硅源科技有限公司 | High-adhesion printing ink |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863846A (en) * | 2011-07-08 | 2013-01-09 | 南昌来捷尔新材料技术有限公司 | Single-component water-based glass screen-printing ink |
| CN104194488A (en) * | 2014-08-28 | 2014-12-10 | 南昌来捷尔新材料技术有限公司 | Single-component waterborne glass ink and preparation method thereof |
| CN105255112B (en) * | 2015-10-29 | 2017-11-21 | 国家纳米科学中心 | A kind of epoxy resin fulvene compounding material and preparation method thereof |
| CN107955471A (en) * | 2017-11-20 | 2018-04-24 | 广东百慕新材料技术工程有限公司 | A kind of special clear priming paint of aqueous one-component and its production technology |
-
2018
- 2018-12-28 CN CN201811618201.2A patent/CN109852136B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109852136A (en) | 2019-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109852136B (en) | Single-component ink and water-based ink coating for 3C glass | |
| CN111793420B (en) | Modified polyaspartic acid ester polyurea coating and preparation method thereof | |
| CN102925041B (en) | Terrace coating and preparation method thereof | |
| CN102732201B (en) | Wear-resistant and weather-resistant epoxy resin coating adhesive and its preparation method | |
| CN107177231B (en) | Photosensitive ink and preparation method and application thereof | |
| CN114045107B (en) | Environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion and preparation method and application thereof | |
| CN111410907A (en) | Self-repairing type temperature-resistant wear-resistant polyaspartic acid ester coating and preparation method thereof | |
| CN111087847A (en) | Electroplating coating silk-screen printing ink and preparation method thereof | |
| CN110669201A (en) | Preparation method and application of waterborne polyurethane emulsion | |
| CN109280470B (en) | Intermediate coating for fiber-reinforced epoxy resin composite material and preparation method thereof | |
| CN109251647B (en) | Water-based primer for fiber-reinforced epoxy resin composite material and preparation method thereof | |
| CN109504165B (en) | Printing ink for two-color anodic oxidation and CNC resistance and application thereof | |
| CN114181611A (en) | Super-water-resistant self-drying glass heat-insulating coating as well as preparation method and application method thereof | |
| CN114806365A (en) | Water-based fluorocarbon coating and coating method thereof | |
| CN114196254A (en) | Bio-based water-based shoe material ink and preparation method thereof | |
| CN113122105A (en) | Organic light-absorbing coating and preparation method thereof | |
| CN109486298B (en) | Fluorocarbon powder coating and preparation method thereof | |
| CN112063289A (en) | UV transparent primer for water-based glaze and preparation method thereof | |
| CN114656837B (en) | High-coverage high-insulation black ink and preparation method thereof | |
| CN112920715B (en) | Protective coating suitable for surfaces of various substrates and preparation method thereof | |
| CN115926600B (en) | Water-based polyurethane coating and preparation method thereof | |
| CN115403980B (en) | Water-based quick-drying antibacterial coating for electronic device, and preparation method and application thereof | |
| CN114410148B (en) | Low-temperature thermosetting 4D hot bending and stretching forming ink and preparation method thereof | |
| CN113930143A (en) | High-solid-content colored transparent coating composition, preparation method and application thereof | |
| CN110591507B (en) | Water-based anticorrosive paint for transformer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 410600 No. 777 North Third Ring Road, Ningxiang County Economic and Technological Development Zone, Changsha City, Hunan Province Patentee after: Matsui New Materials Group Co.,Ltd. Country or region after: China Address before: 410600 No. 777 North Third Ring Road, Ningxiang County Economic and Technological Development Zone, Changsha City, Hunan Province Patentee before: HUNAN SOKAN NEW MATERIALS Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address |