CN113845839A - Color paste compatible inorganic building coating and preparation method thereof - Google Patents
Color paste compatible inorganic building coating and preparation method thereof Download PDFInfo
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- CN113845839A CN113845839A CN202111153595.0A CN202111153595A CN113845839A CN 113845839 A CN113845839 A CN 113845839A CN 202111153595 A CN202111153595 A CN 202111153595A CN 113845839 A CN113845839 A CN 113845839A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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Abstract
The invention discloses a color paste compatible inorganic building coating and a preparation method thereof; the color paste comprises a component A and a component B, wherein the component B is general color paste; the component A comprises the following components in percentage by mass based on the total weight of the component A: siloxane oligomer: 25-30%, water-based acrylic resin: 1-5%, graphene oxide: 0.05-2%, dispersant: 0.2-0.5%, defoamer: 0.2-0.5%, inorganic filler: 25-30%, thickener: 1-2%, deionized water: and (4) the balance. The water-based building coating is a weak acid system, does not influence the stability of color paste, can adopt common general organic color paste on the market for color mixing without flocculation, and has the advantages of good stability, low cost and wide color selection range.
Description
Technical Field
The invention belongs to the technical field of coatings, and relates to a color paste compatible inorganic building coating and a preparation method thereof.
Background
The inorganic building paint is prepared with alkali metal silicate or silica sol as main adhesive, small amount of synthetic resin emulsion, pigment, stuffing, assistant, etc. Silicate paint has excellent non-inflammability, mildew and algae resistance, environmental protection, air permeability, alkali resistance and aging resistance, so that the silicate paint is increasingly widely applied to the field of decoration of indoor and outdoor walls.
However, the pH value of the coating product is also high and can reach 11-12 due to the strong basicity of the alkali metal silicate (the pH value is generally more than 13). If the general organic color paste of the commercial architectural coating is directly used in an inorganic silicate system with higher pH value without adjustment, the alkali metal silicate in the system can destroy a wetting dispersant layer coated on the periphery of the pigment particles of the color paste, so that the pigment particles are directly exposed, the pigment particles are flocculated, the stable system of the color paste is destroyed, the hue index of the color can be slowly changed, the problems of flooding, floating and color change are caused, and the color mixing property is extremely poor.
In order to solve the problems, inorganic pigment color paste is often adopted for color mixing, but the inorganic pigment color paste has insufficient color vividness, poor coloring power and high price; in addition, the variety of the inorganic pigment is few, the color spectrum is incomplete, and a plurality of colors can not be called out by the inorganic pigment, thereby greatly limiting the selection range of the end customer for the colors.
Disclosure of Invention
Aiming at the defects that the inorganic silicate building coating in the prior art is strong in alkalinity, flocculation, caking and thickening are easy to occur when the inorganic silicate building coating is matched with general organic color paste on the market for color mixing, the stability of the color paste is damaged, and the like, the invention provides the color paste compatible inorganic building coating and the preparation method thereof. The inorganic building coating of the invention has weak acidity system, does not influence the stability of color paste, can adopt general organic color paste sold in the market for color mixing without flocculation, and has the characteristics of good stability, low cost and wide color selectable range.
The purpose of the invention is realized by the following technical scheme:
the invention discloses a color paste compatible inorganic building coating composition, which comprises a component A and a component B, wherein the component B is general color paste;
the component A comprises the following components in percentage by mass based on the total weight of the component A:
siloxane oligomer: 25 to 30 percent of the total weight of the mixture,
water-based acrylic resin: 1 to 5 percent of the total weight of the mixture,
and (3) graphene oxide: 0.05 to 2 percent of the total weight of the mixture,
dispersing agent: 0.2 to 0.5 percent of,
defoaming agent: 0.2 to 0.5 percent of,
inorganic filler: 25 to 30 percent of the total weight of the mixture,
thickening agent: 1 to 2 percent of the total weight of the mixture,
deionized water: and (4) the balance.
The paint of the invention is divided into A, B two components, wherein the component B is a color paste part, common color pastes in the market can be used universally, and organic color pastes and inorganic color pastes can be selected freely according to required colors. The paint is divided into two components, so that color paste can be conveniently selected and replaced and the color can be adjusted, and the proper color paste is selected and is directly mixed with the component A after the color is adjusted to the required color, so that the paint is convenient, quick, simple and feasible. A. The two components of B may be used in amounts as is conventional in the art. In some embodiments, the mass ratio of the B component to the A component is 15-25: 75-85.
The paint adopts organic and inorganic composite film forming substances, and the two film forming substances are both acidic, so that the final paint is weakly acidic (pH is 4-5.5), common organic and inorganic color pastes in the market can be compatible, and due to the addition of the graphene oxide with amphipathy, the selection of the color paste is not limited, the organic color paste and the inorganic color paste can be used, the compatibility of the color paste and a paint system is better, and the color phase authenticity is better.
As an embodiment of the present invention, the siloxane oligomer has a pH of 3 to 4 and a degree of polymerization of 20 to 50. The pH value of the prepared coating is high due to overhigh pH value, and the flocculation of the organic color paste is unstable. The polymerization degree is too high, the molecular weight is large, the coating hardness is high, and the coating is easy to crack; low polymerization degree, small molecular weight, poor coating film forming property and insufficient hardness. The siloxane oligomer of the present invention is a film-forming substance, has a molecular weight larger than that of silicone oil, is not limited to dimethyl, and may be one kind of siloxane or a mixture of plural kinds of siloxanes. Including polymethyltrimethoxysilane, polymethyltriethoxysilane, etc.
As an embodiment of the invention, the aqueous acrylic resin is acidic, and acidic groups are connected to the molecular chain; the acidic groups include-COOH, -SO3H. The aqueous acrylic resin includes a methacrylic acid copolymer.
As an embodiment of the invention, the dispersant is a non-ionic dispersant, including tego760W, modesty FX-365, creative zetaspersre 179, and the like.
As an embodiment of the invention, the inorganic filler is selected from one or more of calcined kaolin, heavy calcium, mica powder, fumed silica, silicon whisker and alumina.
As an embodiment of the invention, the antifoam agent is a non-ionic antifoam agent, including basf Foamaster223, modesty DF7005, TEGO Airex 902W, and the like.
As an embodiment of the invention, the thickening agent is selected from one or more of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose and hydroxypropyl methyl cellulose.
As an embodiment of the invention, the coating composition has a pH of 5.5 or less. In some embodiments, the coating composition has a pH of 4 to 5.5.
The invention also relates to a preparation method of the color paste compatible inorganic building coating composition, which comprises the following steps:
s1, mixing graphene oxide with deionized water, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid;
s2, uniformly mixing siloxane oligomer, a dispersing agent, inorganic filler, deionized water, 50-70% of a defoaming agent and graphene oxide dispersion liquid, grinding and filtering to obtain filler slurry;
s3, preparing a thickener into a transparent solution with the concentration of 5-10%, and uniformly mixing the transparent solution with filler slurry, water-based acrylic resin and the balance of a defoaming agent to obtain a component A;
and S4, adding the universal color paste (namely the component B) into the paint obtained in the step S3, and uniformly mixing to obtain the paint composition.
As an embodiment of the present invention, ultrasonic dispersion is performed for 30 to 60min in step S1.
In step S2, the slurry is ground to a fineness of less than 20 μm and filtered through a 300-mesh filter cloth.
Compared with the prior art, the invention has the following beneficial effects:
(1) the water-based building coating is a weak acid system, does not influence the stability of color paste, can adopt common general organic color paste on the market to carry out color mixing without flocculation, and has the advantages of good stability, low cost and wide color selection range;
(2) the graphene oxide added in the invention aims to increase the compatibility of the color paste and the film forming substance, and the stability of the color paste and the authenticity of the hue are better; and due to the amphipathy, the color paste has wide selection range and no limitation;
(3) the coating is divided into A, B components, which is convenient for the selection and replacement of color paste and the adjustment of the color of the coating;
(4) the inorganic building paint has polysiloxane as main filming matter, Si-O-Si inorganic molecular chain, hardness up to 4H, washing resistance up to 10 ten thousand times and excellent performance.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
The invention provides a color paste compatible inorganic building coating and a preparation method thereof;
the color paste compatible inorganic building coating comprises A, B components. The formula is as follows based on 100 percent:
the component A comprises:
siloxane oligomer: 25 to 30 percent of
Water-based acrylic resin: 1 to 5 percent
And (3) graphene oxide: 0.05 to 2 percent
Dispersing agent: 0.2 to 0.5 percent
Defoaming agent: 0.2 to 0.5 percent
Inorganic filler: 25 to 30 percent of
Thickening agent: 1 to 2 percent
Deionized water: balance of
And B component: general color paste: 15 to 25 percent.
Wherein:
siloxane oligomer: the pH value of the main film forming matter is 3-4, the degree of polymerization is 20-50, the degree of polymerization is too small, the coating after curing and film forming has low hardness and poor wear resistance; the polymerization degree is too high, the coating after being cured into a film has high hardness and is easy to crack, and more organic acrylic resin is required to be added for preventing the cracking of the coating, so that the inorganic property, the environmental protection property and the health property of the coating are influenced.
Water-based acrylic resin: acidic, with-COOH, -SO attached to the molecular chain3H and other acidic groups, and auxiliary film-forming substances, so that the flexibility of the coating is improved, and the coating is prevented from cracking.
And (3) graphene oxide: the color paste has amphipathy, namely, the color paste is hydrophilic and oleophilic, the edge of the sheet is rich in oxygen-containing hydrophilic groups, the interior of the sheet has hydrophobicity, and the surface is equivalent to a surfactant, so that the energy between interfaces can be reduced, the compatibility of the color paste and a coating is better, and the universality of the color paste is stronger.
Dispersing agent: non-ionic, and can raise the dispersing effect of pigment and filler.
Inorganic filler: calcined kaolin, coarse whiting, mica powder, fumed silica, whisker silicon and/or alumina.
Defoaming agent: non-ionic, reduces the surface tension of the coating, inhibits foam generation or eliminates foam already generated.
Thickening agent: one of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose and hydroxypropyl methyl cellulose increases the viscosity of the coating and prevents the sagging phenomenon during coating.
General color paste: adjusting the color of the paint, and selecting and replacing a proper color paste according to the color required by the paint.
The preparation steps are as follows:
(1) and (3) dispersing graphene oxide: mixing graphene oxide with a small amount of deionized water, and placing the mixture into ultrasonic waves for dispersion for 30-60min to prepare graphene oxide dispersion liquid;
(2) preparing filler slurry: uniformly mixing siloxane oligomer, a dispersing agent, inorganic filler, deionized water, 50-70% of a defoaming agent and graphene oxide dispersion liquid, grinding the mixture on a grinder until the fineness of the mixture is less than 20 mu m, and filtering the mixture by using 300-mesh filter cloth to obtain filler slurry;
(3) preparing the thickening agent into 5-10% transparent solution for later use;
(4) uniformly mixing the filler slurry, the thickening agent, the acidic acrylic resin and the balance of the defoaming agent, wherein the pH value is less than or equal to 5.5;
(5) and (3) adding the general color paste into the coating obtained in the step (3), and uniformly mixing to obtain the colored inorganic building coating.
The specific application is shown in the following examples:
example 1
The embodiment relates to a color paste compatible inorganic building coating, and the composition and the proportion of the color paste compatible inorganic building coating are shown in Table 1. The preparation method comprises the following steps:
(1) and (3) dispersing graphene oxide: mixing graphene oxide with a small amount of deionized water, and placing the mixture into ultrasonic waves for dispersing for 60min to prepare graphene oxide dispersion liquid;
(2) preparing filler slurry: uniformly mixing siloxane oligomer, a dispersing agent, inorganic filler, deionized water, 60% of defoaming agent and graphene oxide dispersion liquid, grinding the mixture on a grinder until the fineness of the mixture is less than 20 mu m, and filtering the mixture by using 300-mesh filter cloth to obtain filler slurry;
(3) preparing a thickening agent into a transparent solution with the concentration of 10% for later use;
(4) uniformly mixing the filler slurry, the thickening agent, the acidic acrylic resin and 40% of defoaming agent, wherein the pH value is less than or equal to 5.5;
(5) and (4) adding the general color paste into the coating obtained in the step (4), and uniformly mixing to obtain the colored inorganic building coating. Wherein the mass ratio of the universal color paste to the coating is 20: 80.
In the embodiment, the siloxane oligomer is polymethyl trimethoxy silane, the dispersant is tego760W, the inorganic filler is heavy calcium, the defoamer is humble DF7005, the thickener is hydroxyethyl cellulose, the general color paste is WD series color paste of New materials GmbH in Zhejiang Na, and the acidic acrylic resin is methacrylic acid copolymer.
Example 2
The embodiment relates to a color paste compatible inorganic building coating, and the composition and the proportion of the color paste compatible inorganic building coating are shown in Table 1. The preparation method comprises the following steps:
(1) and (3) dispersing graphene oxide: mixing graphene oxide with a small amount of deionized water, and placing the mixture into ultrasonic waves for dispersing for 45min to prepare graphene oxide dispersion liquid;
(2) preparing filler slurry: uniformly mixing siloxane oligomer, a dispersing agent, inorganic filler, deionized water, 70% of defoaming agent and graphene oxide dispersion liquid, grinding the mixture on a grinder until the fineness of the mixture is less than 20 microns, and filtering the mixture by using 300-mesh filter cloth to obtain filler slurry;
(3) preparing the thickening agent into 8% transparent solution for later use;
(4) uniformly mixing the filler slurry, the thickening agent, the acidic acrylic resin and 30% of defoaming agent, wherein the pH value is less than or equal to 5.5;
(5) and (4) adding the general color paste into the coating obtained in the step (4), and uniformly mixing to obtain the colored inorganic building coating. Wherein the mass ratio of the universal color paste to the coating is 15: 85.
In the embodiment, the siloxane oligomer is polymethyl triethoxy silane, the dispersant is moderate FX-365, the inorganic filler is whisker silicon, the defoamer is TEGO Airex 902W, the thickener is hydroxymethyl cellulose, the general color paste is inner and outer wall building coating color paste of Shanghai Baiyan industries Co., Ltd, and the acidic acrylic resin is methacrylic acid copolymer.
Example 3
The embodiment relates to a color paste compatible inorganic building coating, and the composition and the proportion of the color paste compatible inorganic building coating are shown in Table 1. The preparation method comprises the following steps:
(1) and (3) dispersing graphene oxide: mixing graphene oxide with a small amount of deionized water, and placing the mixture into ultrasonic waves for dispersing for 30min to prepare graphene oxide dispersion liquid;
(2) preparing filler slurry: uniformly mixing siloxane oligomer, a dispersing agent, inorganic filler, deionized water, 55% of defoaming agent and graphene oxide dispersion liquid, grinding the mixture on a grinder until the fineness of the mixture is less than 20 microns, and filtering the mixture by using 300-mesh filter cloth to obtain filler slurry;
(3) preparing a thickening agent into a 5% transparent solution for later use;
(4) uniformly mixing the filler slurry, the thickening agent, the acidic acrylic resin and 45% of defoaming agent, wherein the pH value is less than or equal to 5.5;
(5) and (4) adding the general color paste into the coating obtained in the step (4), and uniformly mixing to obtain the colored inorganic building coating. Wherein the mass ratio of the universal color paste to the coating is 25: 75.
In the embodiment, the siloxane oligomer is polymethyltriethoxysilane, the dispersant is lightness FX-365, the inorganic filler is mica powder, the defoamer is Pasfu Foamaster223, the thickener is carboxymethyl cellulose, the general color paste is inner and outer wall building paint color paste of Shanghai Feilau paint company Limited, and the acidic acrylic resin is methacrylic acid copolymer.
Example 4
The embodiment relates to a color paste compatible inorganic building coating, and the composition and the proportion of the color paste compatible inorganic building coating are shown in Table 1. The preparation method comprises the following steps:
(1) and (3) dispersing graphene oxide: mixing graphene oxide with a small amount of deionized water, and placing the mixture into ultrasonic waves for dispersing for 30min to prepare graphene oxide dispersion liquid;
(2) preparing filler slurry: uniformly mixing siloxane oligomer, a dispersing agent, inorganic filler, deionized water, 50% of defoaming agent and graphene oxide dispersion liquid, grinding the mixture on a grinder until the fineness of the mixture is less than 20 microns, and filtering the mixture by using 300-mesh filter cloth to obtain filler slurry;
(3) preparing a thickening agent into a 5% transparent solution for later use;
(4) uniformly mixing the filler slurry, the thickening agent, the acidic acrylic resin and 50% of defoaming agent, wherein the pH value is less than or equal to 5.5;
(5) and (4) adding the general color paste into the coating obtained in the step (4), and uniformly mixing to obtain the colored inorganic building coating. Wherein the mass ratio of the universal color paste to the coating is 18: 82.
In the embodiment, the siloxane oligomer is polymethyl trimethoxy silane, the dispersing agent is Yingxiao Zeta Sperse179, the inorganic filler is calcined kaolin, the defoaming agent is Pasf Foamaster223, the thickening agent is carboxymethyl cellulose, the general color paste is inner and outer wall building coating color paste of Shanghai Feilau paint GmbH, and the acidic acrylic resin is methacrylic acid copolymer.
Comparative example 1
The comparative example relates to an inorganic architectural coating, the composition and formulation of which are shown in table 1. This comparative example is substantially the same as example 4 except that: polydimethylsiloxane is used to replace the polymethyltrimethoxysilane.
Comparative example 2
The comparative example relates to an inorganic architectural coating, the composition and formulation of which are shown in table 1. This comparative example is substantially the same as example 4 except that: a quaternary amine type acrylic resin (Rohm pharmaceutical factory, Germany: Eudragit RL/RS30D) was used instead of the methacrylic copolymer.
Comparative example 3
The comparative example relates to an inorganic architectural coating, the composition and formulation of which are shown in table 1. This comparative example is substantially the same as example 4 except that: the methacrylic acid copolymer is replaced by the waterborne hydroxyl acrylic resin (Shenzhen Qijiashenda polymer materials Co., Ltd., PAR-1622-70).
Comparative example 4
The comparative example relates to an inorganic architectural coating, the composition and formulation of which are shown in table 1. This comparative example is essentially the same as example 4, and is prepared as follows:
(1) preparing filler slurry: uniformly mixing siloxane oligomer, a dispersing agent, inorganic filler, deionized water and 50% of defoaming agent, grinding the mixture on a grinder until the fineness of the mixture is less than 20 mu m, and filtering the mixture by using 300-mesh filter cloth to obtain filler slurry;
(2) preparing a thickening agent into a 5% transparent solution for later use;
(3) uniformly mixing the filler slurry, the thickening agent, the acidic acrylic resin and 50% of defoaming agent, wherein the pH value is less than or equal to 5.5;
(4) and (3) adding the general color paste into the coating obtained in the step (3), and uniformly mixing to obtain the colored inorganic building coating.
TABLE 1
The coatings prepared in the above examples and comparative examples were subjected to the performance test, the test method is shown in table 2, and the test results are shown in tables 3 and 4.
TABLE 2
TABLE 3
TABLE 4
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A color paste compatible inorganic building coating composition is characterized by comprising a component A and a component B, wherein the component B is general color paste;
the component A comprises the following components in percentage by mass based on the total weight of the component A:
siloxane oligomer: 25 to 30 percent of the total weight of the mixture,
water-based acrylic resin: 1 to 5 percent of the total weight of the mixture,
and (3) graphene oxide: 0.05 to 2 percent of the total weight of the mixture,
dispersing agent: 0.2 to 0.5 percent of,
defoaming agent: 0.2 to 0.5 percent of,
inorganic filler: 25 to 30 percent of the total weight of the mixture,
thickening agent: 1 to 2 percent of the total weight of the mixture,
deionized water: and (4) the balance.
2. The color paste compatible inorganic architectural coating composition of claim 1 wherein the siloxane oligomer has a pH of 3 to 4 and a degree of polymerization of 20 to 50.
3. The color paste compatible inorganic architectural coating composition according to claim 1, wherein the aqueous acrylic resin is acidic, and acidic groups are connected to a molecular chain; the acidic groups include-COOH, -SO3H。
4. The color paste compatible inorganic architectural coating composition of claim 1 wherein the dispersant is a non-ionic dispersant.
5. The color paste compatible inorganic architectural coating composition according to claim 1, wherein the inorganic filler is selected from one or more of calcined kaolin, heavy calcium, mica powder, fumed silica, whisker silicon, and alumina.
6. The color paste compatible inorganic architectural coating composition of claim 1 wherein the defoamer is a non-ionic defoamer.
7. The color paste compatible inorganic architectural coating composition according to claim 1, wherein the thickener is one or more selected from the group consisting of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, and hydroxypropyl methyl cellulose.
8. The color paste compatible inorganic architectural coating composition of claim 1 wherein the pH of the coating composition is less than or equal to 5.5.
9. A process for the preparation of a mill base compatible inorganic architectural coating composition according to any of claims 1 to 8, characterized in that it comprises the steps of:
s1, mixing graphene oxide with deionized water, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid;
s2, uniformly mixing siloxane oligomer, a dispersing agent, inorganic filler, deionized water, 50-70% of a defoaming agent and graphene oxide dispersion liquid, grinding and filtering to obtain filler slurry;
s3, preparing a thickener into a transparent solution with the concentration of 5-10%, and uniformly mixing the transparent solution with the filler slurry, the water-based acrylic resin and the balance of the defoaming agent;
s4, adding the universal color paste into the paint obtained in the step S3, and uniformly mixing to obtain the paint composition.
10. The method according to claim 9, wherein the ultrasonic dispersion in step S1 is performed for 30-60 min; in step S2, grinding to fineness less than 20 μm, and filtering.
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Effective date of registration: 20230830 Address after: Room 108, No. 9, Lane 205, Gaoji Road, Sijing Town, Songjiang District, Shanghai, 201601 Patentee after: SHANGHAI EXCILON NEW MATERIALS Co.,Ltd. Address before: Room 108, No. 9, Lane 205, Gaoji Road, Sijing Town, Songjiang District, Shanghai 201600 Patentee before: SHANGHAI EXCILON NEW MATERIALS Co.,Ltd. Patentee before: Shenzhen Aibi glaze New Material Co.,Ltd. |