CN109957967A - A kind of unioresistant finishing agent and its synthetic method - Google Patents
A kind of unioresistant finishing agent and its synthetic method Download PDFInfo
- Publication number
- CN109957967A CN109957967A CN201910207913.3A CN201910207913A CN109957967A CN 109957967 A CN109957967 A CN 109957967A CN 201910207913 A CN201910207913 A CN 201910207913A CN 109957967 A CN109957967 A CN 109957967A
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- China
- Prior art keywords
- finishing agent
- uvioresistant
- synthetic method
- textile
- uvioresistant finishing
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
- C07C235/76—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic System
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/419—Amides having nitrogen atoms of amide groups substituted by hydroxyalkyl or by etherified or esterified hydroxyalkyl groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
Abstract
The present invention relates to a kind of unioresistant finishing agent and its synthetic method, the structures of the uvioresistant finishing agent are as follows:The present invention enriches uvioresistant finishing agent type, energy conservation and environmental protection, and industrialized production and application have a extensive future.
Description
Technical field
The invention belongs to textile chemistry auxiliary agent fields, and in particular to a kind of uvioresistant finishing agent and its synthetic method.
Background technique
In recent years, with the rapid development of scientific and technological level, people have discharged a large amount of fluorine, chlorine compound into atmosphere, add
The acute destruction of ozone layer, keeps the ultraviolet radiation for reaching ground more and more, seriously threatens human health.It is excessive ultraviolet
Beta radiation can damage cornea and crystalline lens, upset human immune system, or even induce cutaneum carcinoma.As resistance ultraviolet radiation
First barrier, and the first layer guarantee to human body radiation protection, the research of anti-ultraviolet fabric just especially important.
The anti-ultraviolet method of textile is generally divided into two kinds, i.e. physical method and chemical method.Physical method refers to that increase fabric is tight
Density and thickness improve fabric color;Chemical method refers to by synthesizing uvioresistant finishing agent, is applied to fabric, is come with this
Reduce damage of the ultraviolet light to human body.Wherein, uvioresistant finishing agent is divided into ultraviolet light screener and ultraviolet absorbing agent again, purple
Outside line screener easily causes the problem of allergy, limits it and is widely used.Currently, common ultraviolet absorbing agent has benzophenone
Class, salicylic acid, benzotriazole, triazines and organic nickel class.
The object of the present invention is to provide a kind of new uvioresistant finishing agent and its synthetic method, the uvioresistants of preparation
Finishing agent has preferable uvioresistant effect.
Summary of the invention
For effective damage of the pre- antiultraviolet to human body, present invention 2,4-DihydroxyBenzophenone and N- methylol third
Acrylamide reaction generates a kind of novel uvioresistant finishing agent.
An object of the present invention is to provide a kind of novel uvioresistant finishing agent.
The second object of the present invention is to provide the synthetic method of the uvioresistant finishing agent.
The third object of the present invention is to provide application of the novel uvioresistant finishing agent in textile finishing process.
To achieve the above object, the present invention adopts the following technical scheme:
The present invention provides a kind of uvioresistant finishing agent, the structures of the uvioresistant finishing agent are as follows:
The present invention also provides the synthetic methods of the uvioresistant finishing agent, comprising the following steps:
A. in the reaction kettle that bath temperature is 60 DEG C, 2,4-DihydroxyBenzophenone, sodium hydroxide (solid) is added;
B. it is passed through nitrogen with vacuum pump, guarantees that oxygen empties;
C. the N hydroxymethyl acrylamide for being dissolved in ethyl alcohol is added in reaction kettle;
D. it is reacted in a nitrogen environment;
E. after reaction, it is cooled to room temperature, discharges.
Preferably, the ratio between amount of substance of N hydroxymethyl acrylamide and 2,4-DihydroxyBenzophenone be (1.0~
2.5): 1.
Preferably, the ratio between amount of substance of sodium hydroxide and 2,4-DihydroxyBenzophenone is 0.005 in the step A:
1。
Preferably, the mass fraction that N hydroxymethyl acrylamide accounts for ethanol solution in step C is 19%~25%.
Preferably, the temperature reacted in step D is 40 DEG C~70 DEG C;Reaction time is 4h~8h.
Preferably, the time interval for nitrogen being passed through in step D is 5~20min.
The present invention also provides application of the above-mentioned uvioresistant finishing agent in textile anti-ultraviolet finishing, especially exist
Application in pure cotton textile.
The present invention also provides a kind of textile finishing working solution, which includes that above-mentioned uvioresistant is whole
Manage agent.
Preferably, which also contains MgCl2·6H2O。
The present invention also provides a kind of textile finishing working solution, the method for the textile finishing working solution by including the following steps
It is prepared: by the unpurified uvioresistant finishing agent of above method preparation, MgCl2·6H2O is uniformly mixed and is prepared into
It arrives.
Preferably, MgCl is used2·6H2The pH of the textile finishing working solution is modulated 7 by O.
The present invention by adopting the above technical scheme, has the advantage that
The present invention enriches uvioresistant finishing agent type, energy conservation and environmental protection, and industrialized production and application have a extensive future.
The present invention is by controlling the ratio between N hydroxymethyl acrylamide and the amount of substance of 2,4 dihydroxyl benzophenone, reacting
System temperature, the reaction time, be passed through nitrogen time interval method, realize unioresistant finishing agent synthesis, synthesis
Method flow is succinct, universal.
Detailed description of the invention:
Fig. 1 is the infrared spectrogram of unioresistant finishing agent prepared by unpurified embodiment 5.
Specific embodiment:
Below with reference to embodiment, the invention will be further described, it should be understood that these embodiments are only used for illustration
Purpose, be in no way intended to limit protection scope of the present invention.
Laboratory apparatus in the present invention is this field conventional equipment.
Except unioresistant finishing agent (innovation of the invention) is self-control in material therefor and chemical reagent of the present invention
Outside, remaining various chemical raw material is commercially available buys.
The synthesis of unioresistant finishing agent of the present invention is by opening the double bond in N- methylol propionyl amide, then with 2,
What the hydroxyl reaction on 4- dihydroxy benaophenonel was completed, the specific steps are as follows:
Embodiment 1
A kind of synthetic method of uvioresistant finishing agent, includes the following steps:
A. in the reaction kettle that bath temperature is 60 DEG C, 2,4-DihydroxyBenzophenone is added, with sodium hydroxide, wherein
The ratio between amount of substance of sodium hydroxide and 2,4 dihydroxyl benzophenone is 0.005:1;
B. it is passed through nitrogen with vacuum pump, guarantees that oxygen empties;
C. the N hydroxymethyl acrylamide for being dissolved in ethyl alcohol is added in reaction kettle, wherein N hydroxymethyl acrylamide accounts for solution
Mass fraction be 19%, the ratio between amount of substance of N hydroxymethyl acrylamide and 2,4-DihydroxyBenzophenone is 2.0:1, is stirred
It mixes uniformly;
D. it is passed through within every 10 minutes a nitrogen, reaction temperature is 60 DEG C, isothermal reaction 5h.
E. it is cooled to room temperature, discharges.
Embodiment 2
A kind of synthetic method of uvioresistant finishing agent, includes the following steps:
A. in the reaction kettle that bath temperature is 60 DEG C, 2,4-DihydroxyBenzophenone is added, with sodium hydroxide, wherein
The ratio between amount of substance of sodium hydroxide and 2,4 dihydroxyl benzophenone is 0.005:1;
B. it is passed through nitrogen with vacuum pump, guarantees that oxygen empties;
C. the N hydroxymethyl acrylamide for being dissolved in ethyl alcohol is added in reaction kettle, wherein N hydroxymethyl acrylamide accounts for solution
Mass fraction be 19%, the ratio between amount of substance of N hydroxymethyl acrylamide and 2,4-DihydroxyBenzophenone is 1.5:1, is stirred
It mixes uniformly;
D. it is passed through within every 10 minutes a nitrogen, reaction temperature is 60 DEG C, isothermal reaction 5h.
E. it is cooled to room temperature, discharges.
Embodiment 3
A kind of synthetic method of uvioresistant finishing agent, includes the following steps:
A. in the reaction kettle that bath temperature is 55 DEG C, 2,4-DihydroxyBenzophenone is added, with sodium hydroxide, wherein
The ratio between amount of substance of sodium hydroxide and 2,4 dihydroxyl benzophenone is 0.005:1;
B. it is passed through nitrogen with vacuum pump, guarantees that oxygen empties;
C. the N hydroxymethyl acrylamide for being dissolved in ethyl alcohol is added in reaction kettle, wherein N hydroxymethyl acrylamide accounts for solution
Mass fraction be 19%, the ratio between amount of substance of N hydroxymethyl acrylamide and 2,4-DihydroxyBenzophenone is 2.0:1, is stirred
It mixes uniformly;
D. it is passed through within every 10 minutes a nitrogen, reaction temperature is 55 DEG C, isothermal reaction 6h.
E. it is cooled to room temperature, discharges.
Embodiment 4
A kind of synthetic method of uvioresistant finishing agent, includes the following steps:
A. in the reaction kettle that bath temperature is 60 DEG C, 2,4-DihydroxyBenzophenone is added, with sodium hydroxide, wherein
The ratio between amount of substance of sodium hydroxide and 2,4 dihydroxyl benzophenone is 0.005:1;
B. it is passed through nitrogen with vacuum pump, guarantees that oxygen empties;
C. the N hydroxymethyl acrylamide for being dissolved in ethyl alcohol is added in reaction kettle, wherein N hydroxymethyl acrylamide accounts for solution
Mass fraction be 19%, the ratio between amount of substance of N hydroxymethyl acrylamide and 2,4-DihydroxyBenzophenone is 2.0:1, is stirred
It mixes uniformly;
D. it is passed through within every 20 minutes a nitrogen, reaction temperature is 60 DEG C, isothermal reaction 5h.
E. it is cooled to room temperature, discharges.
Embodiment 5
A kind of synthetic method of uvioresistant finishing agent, includes the following steps:
A. in the reaction kettle that bath temperature is 60 DEG C, 2,4-DihydroxyBenzophenone is added, with sodium hydroxide, wherein
The ratio between amount of substance of sodium hydroxide and 2,4 dihydroxyl benzophenone is 0.005:1;
B. it is passed through nitrogen with vacuum pump, guarantees that oxygen empties;
C. the N hydroxymethyl acrylamide for being dissolved in ethyl alcohol is added in reaction kettle, wherein N hydroxymethyl acrylamide accounts for solution
Mass fraction be 19%, the ratio between amount of substance of N hydroxymethyl acrylamide and 2,4-DihydroxyBenzophenone is 2.5:1, is stirred
It mixes uniformly;
D. it is passed through within every 10 minutes a nitrogen, reaction temperature is 60 DEG C, isothermal reaction 5h.
E. it is cooled to room temperature, discharges.
The treatment process of one, fabric
The present invention arranges unioresistant finishing agent to cotton fabric.
A. a fritter cotton is taken, is weighed;
B. the cotton immersion of known weight is contained into MgCl2·6H2In the unioresistant finishing agent of O, room temperature is impregnated
2min, two leachings two are rolled;
C. the fabric after arrangement is put into baking oven, in 60 DEG C of preliminary drying 10min, takes out, then bake 3min at 150 DEG C,
?.
Two, henchnmrk tests
UV protection factor UPF: referring to regulation measurement in GB/T 18830-2009;Crease recovery: referring to GB/
T3819-1997 measurement;Ultimate strength: referring to regulation measurement in GB/T 2392.1-2013.
The UV protection factor of 1 unioresistant finishing agent of table
The performance of 2 unioresistant finishing agent of table
Embodiment 5 makes the infrared spectrogram of unioresistant finishing agent by oneself as shown in Figure 1:
As seen from Figure 1, in 3100~3700cm-1The absorption peak at place, which obviously broadens, to time, this is because the suction of c h bond
Caused by receipts vibration performance peak and the absorption vibration performance peak of O-H overlap, in 2976.90cm-1Place is nearby the C-H of phenyl ring
Absorb vibration performance peak, 1625.72cm-1Place is the absorption of vibrations characteristic peak of ketone carbonyl, 1116.2cm-1Place is that C-O-C absorbs vibration
Dynamic characteristic peak, 1447.72cm-1And 1341.59cm-1There is the absorption vibration performance peak of phenyl ring skeleton in place.By result above table
Bright, this two kinds of substances are reacted.
Unioresistant finishing agent prepared by the present invention has preferable uvioresistant effect, and UPF value can reach the effect of 50+
Fruit meets the requirement of anti-ultraviolet fabric, can absorb the ultraviolet light of 280~400nm.
Using unioresistant finishing agent finishing of cotton textiles prepared by the present invention, uvioresistant effect can achieve country
The requirement of textile uvioresistant standard 50+, meets the requirement of uvioresistant finishing agent.
Examples are merely exemplary for the above, and it is not intended to limit the scope of the present invention in any way.Art technology
Personnel should be understood that without departing from the spirit and scope of the invention can details and form to technical solution of the present invention
It modifies or replaces, but these modifications and replacement are each fallen in scope of the invention.
Claims (10)
1. a kind of uvioresistant finishing agent, it is characterised in that: the structure of the uvioresistant finishing agent are as follows:
2. the synthetic method of uvioresistant finishing agent described in claim 1, it is characterised in that: the following steps are included:
A. in the reaction kettle that bath temperature is 60 DEG C, 2,4-DihydroxyBenzophenone, sodium hydroxide is added;
B. it is passed through nitrogen with vacuum pump, guarantees that oxygen empties;
C. the N hydroxymethyl acrylamide for being dissolved in ethyl alcohol is added in reaction kettle;
D. it is reacted in a nitrogen environment;
E. after reaction, it is cooled to room temperature, discharges.
3. the synthetic method of uvioresistant finishing agent according to claim 2, it is characterised in that: N hydroxymethyl acrylamide and
The ratio between amount of substance of 2,4 dihydroxyl benzophenone is (1.0~2.5): 1.
4. the synthetic method of uvioresistant finishing agent according to claim 2, it is characterised in that: hydroxide in the step A
The ratio between amount of substance of sodium and 2,4 dihydroxyl benzophenone is 0.005:1.
5. the synthetic method of uvioresistant finishing agent according to claim 2, it is characterised in that: N- methylol third in step C
The mass fraction that acrylamide accounts for ethanol solution is 19%~25%.
6. the synthetic method of uvioresistant finishing agent according to claim 2, it is characterised in that: the temperature reacted in step D
It is 40 DEG C~70 DEG C;Reaction time is 4h~8h.
7. the synthetic method of uvioresistant finishing agent according to claim 2, it is characterised in that: be passed through nitrogen in step D
Time interval is 5~20min.
8. application of the uvioresistant finishing agent described in claim 1 in textile anti-ultraviolet finishing is especially spun in pure cotton
Application in fabric.
9. a kind of textile finishing working solution, which includes uvioresistant finishing agent described in claim 1;It is excellent
Selection of land, the textile finishing working solution also contain MgCl2·6H2O。
10. a kind of textile finishing working solution, it is characterised in that: the textile finishing working solution is prepared by the method included the following steps
It obtains: by the unpurified uvioresistant finishing agent of any one of claim 2-7 the method preparation, MgCl2·6H2O, stirring
It is uniformly mixed and is prepared.Preferably, MgCl is used2·6H2The pH of the textile finishing working solution is modulated 7 by O.
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CN201910207913.3A CN109957967B (en) | 2019-03-19 | 2019-03-19 | Anti-ultraviolet finishing agent and synthetic method thereof |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113638225A (en) * | 2021-09-23 | 2021-11-12 | 齐齐哈尔大学 | Triazine ultraviolet-resistant finishing agent and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105348131A (en) * | 2015-12-03 | 2016-02-24 | 中国海洋大学 | Reaction type ultraviolet light absorber as well as a preparation method and application thereof |
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Patent Citations (1)
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CN105348131A (en) * | 2015-12-03 | 2016-02-24 | 中国海洋大学 | Reaction type ultraviolet light absorber as well as a preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
秦吉喜等: "含二苯甲酮类高分子水溶性紫外线吸收剂的合成与表征", 《应用化工》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113638225A (en) * | 2021-09-23 | 2021-11-12 | 齐齐哈尔大学 | Triazine ultraviolet-resistant finishing agent and preparation method thereof |
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