CN110615944A - Thermochromic spraying-free polypropylene material and manufacturing method thereof - Google Patents
Thermochromic spraying-free polypropylene material and manufacturing method thereof Download PDFInfo
- Publication number
- CN110615944A CN110615944A CN201910904740.0A CN201910904740A CN110615944A CN 110615944 A CN110615944 A CN 110615944A CN 201910904740 A CN201910904740 A CN 201910904740A CN 110615944 A CN110615944 A CN 110615944A
- Authority
- CN
- China
- Prior art keywords
- parts
- weight
- thermochromic
- powder
- polypropylene material
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a temperature-sensing color-changing spray-free polypropylene material and a manufacturing method thereof, wherein the polypropylene material comprises the following components: 10-80 parts of polypropylene resin, 1-50 parts of filler, 1-5 parts of dispersant EBS, 0.1-5 parts of colorant, 0.32-10 parts of toughener POE1, 0.1-0.3 part of antioxidant, 0.1-0.5 part of liquid coupling agent, 0.1-20 parts of pearlescent pigment or metal powder and 0.1-1 part of temperature-sensitive color-changing powder. The manufacturing method comprises the following steps: the filler, the liquid coupling agent and the dispersant EBS are ground in a high-speed grinder, and the pearlescent pigment or the metal powder is added into the liquid coupling agent. The polypropylene, the auxiliary agent, the pigment and the filler subjected to micronization treatment are premixed according to a certain proportion by adopting a double-screw extruder blending method. The invention is prepared by extrusion, cooling, grain cutting and packaging. The invention has the beneficial effects that: the invention provides a practical thermochromic spraying-free polypropylene material which has low shrinkage and deformation, strong pearl luster and flashing effect and changes color along with temperature.
Description
Technical Field
The invention relates to the field of plastic production and processing, in particular to a thermochromic spraying-free polypropylene material and a manufacturing method thereof.
Background
The polypropylene resin can achieve the special effect of flickering after being added with mica pearlescent pigment, aluminum silver powder, copper powder and the like, the pearlescent pigment is generally formed by coating mica with a metal oxide thin layer, and the mica is widely applied to the fields of household appliances, automobile interior and exterior decorations, electronic products, hardware tools, packaging materials and the like, the paint spraying process is reduced, the cost is saved, and the polypropylene resin has wide market prospect. However, the effect has a defect in injection molding that flow marks appear at a sprue to influence the appearance of a product, and meanwhile, certain filling materials are added into some products to ensure the material shrinkage and deformation of the products, so that the flickering effect of the products is deteriorated, and the use value of the products is reduced. The temperature sensing is discoloured and has further enlarged the use attribute of material, shows different colours at different temperatures, and is dazzling more visually and directly seeing.
Chinese patent document CN103242616A, application date 2013.04.27, discloses an aesthetic resin composition with fantasy colors and a preparation method thereof, wherein the aesthetic resin composition comprises the following components in parts by weight: 100 parts of thermoplastic resin, 0.1-5.0 parts of special-shaped hollow glass beads, 0.1-3.0 parts of lubricant and 0.1-1.0 part of antioxidant, and the preparation method comprises the following steps: mixing the components in a high-speed mixer, feeding the mixture into a double-screw extruder, melting and compounding the mixture under the conditions of conveying, shearing and mixing, extruding, drawing strips, cooling and granulating to obtain the composite material. The application has a good colorful effect, can avoid spraying, and can be widely applied to the fields of automobiles, household appliances, consumer electronics, electronic appliances, home decoration and the like with high requirements on appearance.
Chinese patent document CN102942742A, application date 2012.12.04, discloses a spray-free PP material with high gloss and metallic or pearlescent glittering effect and a preparation method thereof, which is composed of the following substances by weight percentage: PP97-99%, antioxidant 1680.1-0.3%, antioxidant 10100.1-0.5%, lubricating dispersant TAF 0.1-1%, effect pigment 0.3-1.5%, the PP material of the invention also has the advantage of obtaining good high gloss and pearly luster glittering effect without spraying paint, but the PP material is pure polypropylene material plus effect pigment, the product is easy to deform, the shrinkage rate of the product is higher, and the product is easy to deform.
Chinese patent document CN107841049A, application date 2017.01.12, discloses a thermochromic polypropylene composition, and a preparation method and application thereof, wherein the thermochromic polypropylene composition is composed of the following materials by weight percent: the invention also discloses a preparation method of the thermochromic microcapsule, which comprises the following steps of (1) 95-99% of PP and 0.5-3% of thermochromic microcapsule, wherein the PP material also has the advantage of long-term aging resistance and thermochromic property, but the PP material is a pure polypropylene material and a thermochromic pigment, and the application field of products is not wide.
At present, polypropylene materials with a spray-free effect are difficult to achieve low shrinkage and low deformation, and the addition of a filler to the polypropylene materials can affect the glittering effect of the materials when the shrinkage of the materials is reduced, so how to create a polypropylene material with low shrinkage, low deformation, high gloss, glittering effect and thermochromic performance is an important research and development subject at present.
Disclosure of Invention
The invention aims to provide a practical thermochromic spraying-free polypropylene material which has low shrinkage and deformation, strong pearl gloss and glittering effect and changes color along with temperature.
In order to achieve the above object, the present invention is realized by: the thermochromic spraying-free polypropylene material is characterized by comprising the following components in parts by weight:
10-80 parts of polypropylene resin
1-50 parts of filler
Dispersant EBS1-5
0.1-5% of colorant
Toughening agent POE1-10
0.1-0.3% of antioxidant
Liquid coupling agent 0.1-0.5
0.1-20 parts of pearlescent pigment or metal powder
0.1-1 parts of temperature-sensitive color-changing powder
Further, the components comprise the following components in parts by weight: 30-50 parts of polypropylene, 10-50 parts of filler, 1-4 parts of dispersant EBS, 0.2-0.6 part of colorant, 3-5 parts of toughener POE, 0.1-0.3 part of antioxidant, 0.1-0.5 part of coupling agent, 0.1-10 parts of pearlescent pigment or metal powder and 0.1-1 part of temperature-sensitive color-changing powder.
Further, 65 parts by weight of polypropylene, 25 parts by weight of filler, 3 parts by weight of dispersant EBS, 0.4 part by weight of colorant, 4 parts by weight of toughener POE, 0.2 part by weight of antioxidant, 0.3 part by weight of coupling agent, 2 parts by weight of pearlescent pigment or metal powder and 0.5 part by weight of temperature-sensitive color-changing powder.
The thermochromic spraying-free polypropylene material is characterized in that the filler is one or more of talcum powder, barium sulfate, mica powder, wollastonite, sodium sulfate and glass beads, the antioxidant is pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionate, the coupling agent is a titanate coupling agent, the toughening agent is POE, and the pearlescent pigment is one or more of mica pearlescent pigments with various colors.
The invention also provides a manufacturing method of the thermochromic spraying-free polypropylene material, which comprises the following specific production processes:
in the first step, the filler is micronized: mixing the filler, the coupling agent and the dispersant EBS, and then grinding by adopting a high-speed grinder to activate the surface of the filler; can fully fuse the filler and the polypropylene resin and reduce the shielding pearl powder.
Secondly, directionally coupling the pearlescent pigment or the metal powder: dissolving pearlescent pigment or metal powder into a liquid coupling agent, and using an electromagnetic director to directionally arrange the pearlescent pigment or the metal powder; to achieve a more intense flashing effect.
Thirdly, premixing the polypropylene and the filler subjected to micronization treatment in a high-speed stirrer according to a certain ratio by adopting a double-screw extruder blending method;
and fourthly, adding the mixed material into a double-screw extruder under the conditions of conventional feeding speed, specific temperature and screw rotating speed, adding the directionally coupled pearlescent pigment or the mixture of the metal powder and the thermochromic powder into the double-screw extruder from the front section of the double-screw extruder by using an automatic metering pump, and carrying out extrusion, cooling, grain cutting and packaging.
Compared with the prior art, the thermochromic spraying-free polypropylene material has the outstanding advantages that:
1. the invention effectively improves the shrinkage rate and the deformation rate of the polypropylene material by adding the filler subjected to micronization treatment, has lower shrinkage rate, is not easy to deform, and has small influence on the pearl effect.
2. The pearl luster or metallic luster dazzling effect of the product surface is improved by carrying out directional coupling on the pearl pigment or the metallic powder.
3. The invention ensures that the pearlescent pigment or the metal powder is not sheared strongly and the flashing effect is lost by adding the pearlescent pigment or the metal powder from the front section of the double-screw extruder by an automatic metering pump.
4. The invention ensures the thermochromic effect of the material through a specific processing technology.
5. The invention greatly simplifies the production process of manufacturers, reduces the paint spraying procedures, reduces the cost and improves the paint falling phenomenon of products.
Detailed Description
For better understanding and implementation, the thermochromic spray-free polypropylene material and the manufacturing method thereof according to the present invention will be described in detail with reference to the following examples.
Example l
50 parts of polypropylene, 40 parts of filler, 1 part of dispersant EBS, 0.2 part of colorant, 10 parts of toughener POE, 0.3 part of antioxidant, 0.5 part of liquid coupling agent, 25 parts of pearlescent pigment or metal powder and 1 part of temperature-sensitive color-changing powder are accurately weighed. Grinding the filler, the liquid coupling agent and the dispersant EBS in a high-speed grinder to activate the surface of the filler, adding the pearlescent pigment or the metal powder into the liquid coupling agent, and aligning the pearlescent pigment by using an electromagnetic aligner. The polypropylene, the auxiliary agent, the pigment and the filler subjected to micronization treatment are premixed in a high-speed mixer according to a certain proportion by adopting a double-screw extruder blending method. Adding the mixture into a double-screw extruder under the conditions of conventional feeding speed, specific temperature and screw rotating speed, adding directionally coupled pearlescent pigment or metal powder and thermochromic powder mixture into the double-screw extruder from the front section of the double-screw extruder by using an automatic metering pump, and extruding, cooling, granulating and packaging to obtain the thermochromic spraying-free polypropylene material.
Preferably, the filler is one or a combination of more of talcum powder, barium sulfate, mica powder, wollastonite, sodium sulfate, glass beads and the like, and the pearlescent pigment is mica pearlescent pigment with various colors.
Example 2
Accurately weighing 35 parts by weight of polypropylene, 30 parts by weight of filler, 3 parts by weight of dispersant EBS, 0.4 part by weight of colorant, 4 parts by weight of toughener POE, 0.2 part by weight of antioxidant, 0.3 part by weight of liquid coupling agent, 10 parts by weight of pearlescent pigment or metal powder and 1 part by weight of temperature-sensitive color-changing powder. Grinding the filler, the liquid coupling agent and the dispersant EBS in a high-speed grinder to activate the surface of the filler, adding the pearlescent pigment or the metal powder into the liquid coupling agent, and aligning the pearlescent pigment by using an electromagnetic aligner. The polypropylene, the auxiliary agent, the pigment and the filler subjected to micronization treatment are premixed in a high-speed mixer according to a certain proportion by adopting a double-screw extruder blending method. Adding the mixture into a double-screw extruder under the conditions of conventional feeding speed, specific temperature and screw rotating speed, adding directionally coupled pearlescent pigment or metal powder and thermochromic powder mixture into the double-screw extruder from the front section of the double-screw extruder by using an automatic metering pump, and extruding, cooling, granulating and packaging to obtain the thermochromic spraying-free polypropylene material.
Example 3
Accurately weighing 75 parts by weight of polypropylene, 15 parts by weight of filler, 5 parts by weight of dispersant EBS, 1.0 part by weight of colorant, 1 part by weight of toughener POE, 0.3 part by weight of antioxidant, 0.1 part by weight of liquid coupling agent and 1 part by weight of pearlescent pigment or metal powder. Grinding the filler, the liquid coupling agent and the dispersant EBS in a high-speed grinder to activate the surface of the filler, adding the pearlescent pigment or the metal powder into the liquid coupling agent, and aligning the pearlescent pigment by using an electromagnetic aligner. The polypropylene, the auxiliary agent, the pigment and the filler subjected to micronization treatment are premixed in a high-speed mixer according to a certain proportion by adopting a double-screw extruder blending method. Adding the mixture into a double-screw extruder under the conditions of conventional feeding speed, specific temperature and screw rotating speed, adding directionally coupled pearlescent pigment or metal powder and thermochromic powder mixture into the double-screw extruder from the front section of the double-screw extruder by using an automatic metering pump, and extruding, cooling, granulating and packaging to obtain the thermochromic spraying-free polypropylene material.
Example 4
The main difference between this example and example 1 is that the extrusion process conditions are as follows: the first zone is 90-100 ℃, the second zone is 150-180 ℃, the third zone is 170-180 ℃, and the fourth zone is 175-180 ℃; the five zone is 180 ℃ minus 182 ℃, the six zone is 180 ℃ minus 182 ℃, the seven zone is 180 ℃ minus 185 ℃, the retention time is 1-2 minutes, and the pressure is 10-15 MPa.
Performance evaluation method and implementation standard:
the granulated particle material is dried in a blast oven at 70-80 deg.c for 1-2 hr and then injection molded in an injection molding machine to form the product.
And (4) visually evaluating the pearlescent dazzling effect, and evaluating the change condition of the color along with the temperature by using a high-low temperature test box.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention in any way, and it will be apparent to those skilled in the art that the above description of the present invention can be applied to various modifications, equivalent variations or modifications without departing from the spirit and scope of the present invention.
Claims (8)
1. The thermochromic spraying-free polypropylene material is characterized by comprising the following components:
10-80 parts of polypropylene resin
1-50 parts of filler
Dispersant EBS1-5
0.1-5% of colorant
Toughening agent POE1-10
0.1-0.3% of antioxidant
Liquid coupling agent 0.1-0.5
0.1-20 parts of pearlescent pigment or metal powder
0.1-1 parts of temperature-sensitive color-changing powder
Wherein the contents of all the components are in parts by weight.
2. The thermochromic spray-free polypropylene material according to claim 1, which is composed of the following components in parts by weight: 30-80 parts of polypropylene, 20-50 parts of filler, 2-4 parts of dispersant EBS, 0.2-0.6 part of colorant, 0.1-0.3 part of flexibilizer POE3-5 parts, 0.1-0.3 part of antioxidant, 0.1-0.5 part of liquid coupling agent, 5-15 parts of pearlescent pigment or metal powder and 0.1-1 part of temperature-sensitive color-changing powder.
3. The thermochromic spray-free polypropylene material according to claim 1, wherein the polypropylene is 70 parts by weight, the filler is 22 parts by weight, the dispersant EBS is 1 part by weight, the colorant is 1 part by weight, the toughening agent POE is 5 parts by weight, the antioxidant is 0.2 part by weight, the liquid coupling agent is 0.3 part by weight, the pearlescent pigment or metal powder is 1 part by weight, and the thermochromic powder is 0.5 part by weight.
4. The thermochromic spray-free polypropylene material of claim i, wherein: the filler is one or a combination of more of talcum powder, barium sulfate, mica powder, wollastonite, sodium sulfate and glass beads.
5. The thermochromic spray-free polypropylene material according to claim 1, wherein: the pearlescent pigment is one or a combination of several kinds of mica pearlescent pigments with various colors, and the effect is better due to the combination of several kinds of pearlescent pigments.
6. The thermochromic spray-free polypropylene material according to claim 1, wherein: the temperature sensing color changing powder can change color in a single temperature zone or in a plurality of temperature zones.
7. The method for producing a thermochromic spray-free polypropylene material according to claim 1, comprising the steps of:
putting the filler, the coupling agent and the dispersant EBS into a high-speed grinder for grinding, and applying 100 ℃ for micronization pretreatment; dissolving pearlescent pigment or metal powder into a liquid coupling agent, and using an electromagnetic director to directionally arrange the pearlescent pigment or the metal powder; polypropylene, other additives, pigment and micronized filling agent are premixed in a high-speed mixer for more than 10 minutes by adopting a double-screw extruder blending method; then adding the mixture into a double-screw extruder under the conditions of conventional feeding speed and screw rotating speed, and controlling the processing temperature of the double-screw extruder within 185 ℃; fully and uniformly stirring the directional pearlescent pigment or the metal powder and the thermochromic powder; and adding the directional coupled pearlescent pigment or metal powder and thermochromic powder mixture into the double-screw extruder from the front section of the double-screw extruder by an automatic metering pump according to the weight percentage ratio, and then extruding, cooling, granulating and packaging.
8. The manufacturing method of the thermochromic spray-free polypropylene material according to claim 7, wherein the extrusion process conditions are as follows: the first zone is 90-100 ℃, the second zone is 150-180 ℃, the third zone is 175-180 ℃, and the fourth zone is 180-185 ℃; the fifth to seventh zones are 180 ℃ and 182 ℃, the head temperature is 185 ℃, the retention time is 1 to 2 minutes, and the pressure is 2 to 15 Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910904740.0A CN110615944A (en) | 2019-09-24 | 2019-09-24 | Thermochromic spraying-free polypropylene material and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910904740.0A CN110615944A (en) | 2019-09-24 | 2019-09-24 | Thermochromic spraying-free polypropylene material and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110615944A true CN110615944A (en) | 2019-12-27 |
Family
ID=68924276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910904740.0A Pending CN110615944A (en) | 2019-09-24 | 2019-09-24 | Thermochromic spraying-free polypropylene material and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110615944A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548565A (en) * | 2020-06-23 | 2020-08-18 | 四川中烟工业有限责任公司 | Biaxially oriented polypropylene film with temperature change effect and preparation method thereof |
| CN112080070A (en) * | 2020-09-03 | 2020-12-15 | 金旸（厦门）新材料科技有限公司 | High glow-wire flame-retardant reversible color-changing PP material and preparation method thereof |
| CN115449182A (en) * | 2022-10-24 | 2022-12-09 | 刘玉龙 | Low-temperature color-changeable material for cosmetic packaging and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194124A (en) * | 2014-09-12 | 2014-12-10 | 江苏旭华圣洛迪建材有限公司 | Thermochromic wood-plastic material and preparation method thereof |
| CN104530569A (en) * | 2015-01-30 | 2015-04-22 | 山东道恩高分子材料股份有限公司 | Environment-friendly high-glossiness colorful polypropylene material and manufacturing method thereof |
-
2019
- 2019-09-24 CN CN201910904740.0A patent/CN110615944A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194124A (en) * | 2014-09-12 | 2014-12-10 | 江苏旭华圣洛迪建材有限公司 | Thermochromic wood-plastic material and preparation method thereof |
| CN104530569A (en) * | 2015-01-30 | 2015-04-22 | 山东道恩高分子材料股份有限公司 | Environment-friendly high-glossiness colorful polypropylene material and manufacturing method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548565A (en) * | 2020-06-23 | 2020-08-18 | 四川中烟工业有限责任公司 | Biaxially oriented polypropylene film with temperature change effect and preparation method thereof |
| CN112080070A (en) * | 2020-09-03 | 2020-12-15 | 金旸（厦门）新材料科技有限公司 | High glow-wire flame-retardant reversible color-changing PP material and preparation method thereof |
| CN115449182A (en) * | 2022-10-24 | 2022-12-09 | 刘玉龙 | Low-temperature color-changeable material for cosmetic packaging and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110615944A (en) | Thermochromic spraying-free polypropylene material and manufacturing method thereof | |
| CN113416372B (en) | Spraying-free metallic high-gloss high-weather-resistance PMMA/ASA alloy material and preparation method thereof | |
| CN103881349A (en) | Highly weather-resistant colored polycarbonate-acrylonitrile-butadiene-styrene resin blending material and preparation method thereof | |
| CN108559175B (en) | Spraying-free polypropylene material with black and white marble textures and preparation method thereof | |
| CN113683876A (en) | Spraying-free high-flow high-impact flame-retardant PC material with metal texture and preparation method and application thereof | |
| CN108976693A (en) | A kind of marbling Masterbatch and its application method suitable for ABS | |
| CN104530569A (en) | Environment-friendly high-glossiness colorful polypropylene material and manufacturing method thereof | |
| CN114163797B (en) | Yellow polycarbonate/styrene resin alloy composition and preparation method and application thereof | |
| CN108690264A (en) | A kind of polypropylene material and preparation method thereof of low gloss, anti-tiger fur line injection defect | |
| CN109503922B (en) | Preparation method of pigment functional master batch, product and application thereof | |
| CN109320935B (en) | Production process for improving polycarbonate alloy material color powder point | |
| CN109181092A (en) | It is a kind of to exempt from spraying, the automobile-used outer plaque PP composite material with argentine effect and preparation method thereof | |
| WO2024124871A1 (en) | Wear-resistant spray-free pc/pbt alloy material, preparation method therefor and use thereof | |
| CN113831642B (en) | Application of basalt fiber in spraying-free polypropylene material, composition of basalt fiber and preparation method of composition | |
| CN104177792B (en) | PET multi-functional light master batch | |
| CN112778753B (en) | PA6/PA56 silver flow apparent material and preparation method thereof | |
| CN108623902A (en) | A kind of metal of high glaze or the polypropylene alloy and preparation method thereof of pearl effect | |
| CN109082004A (en) | A kind of Novel free sprayed on material and preparation method thereof | |
| CN111925621A (en) | High-gloss weather-resistant stone-grain-like composition and preparation method thereof | |
| CN112552638A (en) | White ABS composite material with transmittance and preparation method thereof | |
| CN110551361A (en) | special transparent master batch for barium sulfate-based ABS and preparation method thereof | |
| CN109910256A (en) | A kind of preparation method of plastic-metal product | |
| CN107163491B (en) | Modified ABS material, preparation method and application | |
| JP2013216729A (en) | Colored compound, injection molding and decoration part having metallic feeling, and house electric appliance using decoration part | |
| CN116640382B (en) | Spraying-free material and preparation method and application 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191227 |
|
| RJ01 | Rejection of invention patent application after publication |