CN107987760B - Environment-friendly adhesive and preparation method and application thereof - Google Patents
Environment-friendly adhesive and preparation method and application thereof Download PDFInfo
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- CN107987760B CN107987760B CN201711128898.0A CN201711128898A CN107987760B CN 107987760 B CN107987760 B CN 107987760B CN 201711128898 A CN201711128898 A CN 201711128898A CN 107987760 B CN107987760 B CN 107987760B
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, and relates to a novel environment-friendly adhesive as well as a preparation method and application thereof, wherein the novel environment-friendly adhesive comprises 15-50 parts of a thermoplastic elastomer, 2-15 parts of poly α -methyl styrene resin, 1-20 parts of tackifying resin, 15-50 parts of a solvent, 15-50 parts of granular powder, 0.2-2 parts of an antioxidant, 0.2-1 part of a thixotropic agent, 0.4-1.5 parts of a reinforcing agent and 0.5-1 part of titanium dioxide.
Description
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to a novel environment-friendly adhesive as well as a preparation method and application thereof. More specifically, the novel environment-friendly adhesive disclosed by the invention can be simultaneously applied to the fields of structural sealing and bonding.
Background
With the development of society, adhesives have penetrated into various industries and play an important role in various fields. As adhesives are used more and more in various fields, the requirements for adhesives are also higher and higher, in particular in the field of structural sealing or bonding.
Adhesives used in the field of structural sealing or bonding are two adhesives with completely different properties. When the adhesive is used in the field of structural sealing, the adhesive is required to have good stretchability, and when the adhesive is used in the field of bonding, the adhesive is required to have good bonding property. At present, no adhesive with good stretchability and good bonding property is available on the market, so that the adhesive on the market cannot be applied to the fields of structural sealing and bonding at the same time. In addition, adhesives used in the field of structural sealing or in the field of bonding present some significant drawbacks. Adhesives used in the field of structural sealing are the general silicone adhesives, such as glass cement. The adhesive has good stretchability, but has low bonding strength, is slow to cure (especially in winter), is easy to mildew (namely, black spots occur due to growth of microorganisms such as fungi on the surface of the adhesive), and seriously influences the attractiveness of products and the service life of the adhesive especially in wet environments such as kitchens, bathrooms and the like. In addition, part of the auxiliary used in the silicone adhesive can migrate to the bonded material, causing material pollution. Although the structural sealant of polyurethane has excellent performance, the structural sealant of polyurethane has high price and poor universality, and can only be used in high-end special industries. The adhesive used in the bonding field, such as SBS type nail-free adhesive, has good bonding property, but has high hardness, poor toughness and elasticity, poor water resistance, poor aging resistance, poor weather resistance and no tensile strength, and is not suitable for the structural sealing field. Therefore, the development of the adhesive which can be simultaneously applied to the fields of structural sealing and bonding has important practical significance.
Disclosure of Invention
In order to solve the defects that the adhesive in the prior art cannot be simultaneously applied to the field of structural sealing and bonding and other problems, the invention provides a novel environment-friendly adhesive. The novel environment-friendly adhesive disclosed by the invention has good stretchability and good bonding property, and can meet the requirements of the field of structural sealing and bonding at the same time. In addition, the novel environment-friendly adhesive disclosed by the invention is high in curing efficiency, good in mildew resistance and weather resistance, and water-resistant and aging-resistant, and is an adhesive with excellent performance and wide application range.
The invention is realized by the following technical scheme:
a novel environment-friendly adhesive comprises the following components in parts by weight:
preferably, the thermoplastic elastomer is one or a mixture of two of styrene-butadiene-styrene block copolymer and styrene-isoprene-styrene block copolymer.
Further preferably, the thermoplastic elastomer is a styrene-isoprene-styrene block copolymer.
Preferably, the tackifying resin is one or more of modified rosin resin, terpene resin, petroleum resin, alkyl phenolic resin, chlorinated polypropylene resin, polyvinyl chloride resin, aldehyde ketone resin and coumarone resin.
Further preferably, the tackifying resin is one or a mixture of more of chlorinated polypropylene resin and C9 petroleum resin.
Preferably, the solvent is one or more of cyclohexane, methyl acetate, ethyl acetate, dimethyl carbonate, 120# solvent oil, 6# solvent oil, acetone, toluene and dichloromethane.
Further preferably, the solvent is toluene, 120# solvent oil, methyl acetate and dichloromethane in a mass ratio of 0.1-0.25: 0.2-0.5: 0.25-0.4: 0-0.1 of a mixture.
Preferably, the granular powder is one or a mixture of more of light calcium carbonate, barium sulfate, talcum powder, mica powder and kaolin.
Further preferably, the granular powder is light calcium carbonate.
Preferably, the antioxidant is one of a compound or a composite oxidant of an aromatic amine antioxidant, a hindered phenol antioxidant, a thiodipropionic acid diester antioxidant and a phosphite antioxidant.
Further preferably, the antioxidant is a hindered phenol antioxidant.
Preferably, the thixotropic agent is one of organic bentonite, fumed silica, metal soap and hydrogenated castor oil.
Further preferably, the thixotropic agent is fumed silica.
Preferably, the reinforcing agent is one of carbon black, white carbon black, silicate, active calcium carbonate and zinc oxide,
further preferably, the reinforcing agent is white carbon black.
Preferably, the titanium dioxide is one or a mixture of rutile type titanium dioxide, anatase type titanium dioxide and brookite type titanium dioxide.
Further preferably, the titanium dioxide is anatase titanium dioxide.
The invention also provides a preparation method of the novel environment-friendly adhesive, which comprises the following steps:
(1) putting the thermoplastic elastomer and the poly α -methyl styrene resin into an internal mixer together, melting and mixing for 3-8 minutes, extruding and molding to prepare particles;
(2) adding a solvent into a reaction vessel, adding tackifying resin and an antioxidant under the stirring condition, and stirring until the tackifying resin and the antioxidant are dissolved uniformly;
(3) adding the particles prepared in the step (1) under the stirring condition, and stirring until the particles are uniformly dissolved;
(4) and adding granular powder, a reinforcing agent, a thixotropic agent and titanium dioxide, stirring until the mixture is uniformly mixed, and discharging to obtain the novel environment-friendly adhesive.
Preferably, the internal mixer temperature is 130-.
The invention also provides application of the novel environment-friendly adhesive, and the novel environment-friendly adhesive can be simultaneously applied to the fields of structural sealing and bonding.
The invention has the beneficial effects that:
(1) the solvents used in the invention are all low-toxicity environment-friendly or non-toxic environment-friendly solvents, the content of volatile organic matters in the product can be obviously reduced, the indexes of the volatile organic matters meet the standard requirements of GB33372-2016, and the harmfulness of the adhesive to human bodies and the environment is reduced to the minimum;
(2) the adhesive disclosed by the invention is flexible and elastic, large in tensile modulus, high in bonding strength, good in mildew resistance and weather resistance, water-resistant and aging-resistant, and good in sealing performance;
(3) the adhesive disclosed by the invention is low in production cost and quick in curing, has good flexibility, elasticity, water resistance, aging resistance and sealing performance of a general silicone structure sealant, has high bonding strength of a structure assembly adhesive (commonly called a nail-free adhesive), overcomes the defects that the silicone structure sealant is easy to mildew, low in bonding strength and not resistant to aging, and has no stretchability and elastic toughness when the nail-free adhesive is used as the sealant, and can be simultaneously applied to the requirements of the field of structure sealing and the field of bonding.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1
The novel environment-friendly adhesive comprises, by weight, 22 parts of styrene-isoprene-styrene segmented copolymer, 2 parts of poly α -methyl styrene resin, 11.5 parts of C9 petroleum resin, 4 parts of toluene, 10 parts of methyl acetate, 9 parts of 120# solvent oil, 2 parts of dichloromethane, 37 parts of light calcium carbonate, 2640.5 parts of antioxidant BHT, 0.2 part of fumed silica, 0.8 part of white carbon black and 1 part of anatase titanium dioxide.
The preparation method of the novel environment-friendly adhesive comprises the following steps:
(1) placing styrene-isoprene-styrene block copolymer and poly α -methylstyrene resin into an internal mixer with the temperature of 150 ℃ for melting and mixing for 5min, and extruding and molding to prepare particles;
(2) adding toluene, methyl acetate, 120# solvent oil and dichloromethane into a reaction vessel, adding C9 petroleum resin and antioxidant BHT264 under the condition of stirring, and stirring until the mixture is dissolved uniformly;
(3) adding the particles prepared in the step (1) under the stirring condition, and stirring until the particles are uniformly dissolved;
(4) adding light calcium carbonate, white carbon black, fumed silica and anatase titanium dioxide, stirring until the mixture is uniformly mixed, and discharging to obtain the calcium carbonate-titanium dioxide-titanium white powder.
Example 2
The novel environment-friendly adhesive comprises, by weight, 22 parts of a styrene-isoprene-styrene block copolymer, 8 parts of poly α -methylstyrene resin, 5.5 parts of C9 petroleum resin, 4 parts of toluene, 10 parts of methyl acetate, 9 parts of 120# solvent oil, 2 parts of dichloromethane, 37 parts of light calcium carbonate, 2640.5 parts of an antioxidant BHT, 0.2 part of organic bentonite, 0.8 part of zinc oxide and 1 part of rutile type titanium dioxide.
The preparation method of the novel environment-friendly adhesive comprises the following steps:
(1) placing styrene-isoprene-styrene block copolymer and poly α -methylstyrene resin into an internal mixer with the temperature of 140 ℃ for melting and mixing for 5min, and extruding and molding to prepare particles;
(2) adding toluene, methyl acetate, 120# solvent oil and dichloromethane into a reaction vessel, adding C9 petroleum resin and antioxidant BHT264 under the condition of stirring, and stirring until the mixture is dissolved uniformly;
(3) adding the particles prepared in the step (1) under the stirring condition, and stirring until the particles are uniformly dissolved;
(4) adding light calcium carbonate, organic bentonite, zinc oxide and rutile titanium dioxide, stirring until the materials are uniformly mixed, and discharging to obtain the calcium carbonate.
Example 3
The novel environment-friendly adhesive comprises, by weight, 20 parts of styrene-isoprene-styrene segmented copolymer, 8 parts of poly α -methyl styrene resin, 5.5 parts of C9 petroleum resin, 2 parts of chlorinated polypropylene resin, 4 parts of toluene, 10 parts of methyl acetate, 9 parts of No. 120 solvent oil, 2 parts of dichloromethane, 37 parts of light calcium carbonate, 2640.5 parts of antioxidant BHT, 0.2 part of hydrogenated castor oil, 0.8 part of active calcium carbonate and 1 part of anatase titanium dioxide.
The preparation method of the novel environment-friendly adhesive comprises the following steps:
(1) placing styrene-isoprene-styrene block copolymer and poly α -methylstyrene resin into an internal mixer with the temperature of 140 ℃ for melting and mixing for 5min, and extruding and molding to prepare particles;
(2) adding toluene, methyl acetate, No. 120 solvent oil and dichloromethane into a reaction vessel, adding C9 petroleum resin, chlorinated polypropylene resin and antioxidant BHT264 under the condition of stirring, and stirring until the materials are uniformly dissolved;
(3) adding the particles prepared in the step (1) under the stirring condition, and stirring until the particles are uniformly dissolved;
(4) adding light calcium carbonate, hydrogenated castor oil, active calcium carbonate and anatase titanium dioxide, stirring to mix uniformly, and discharging to obtain the product.
Example 4
The novel environment-friendly adhesive comprises the following components, by weight, 16 parts of styrene-isoprene-styrene segmented copolymer, 8 parts of poly α -methylstyrene resin, 5.5 parts of C9 petroleum resin, 6 parts of chlorinated polypropylene resin, 4 parts of toluene, 10 parts of methyl acetate, 9 parts of No. 120 solvent oil, 2 parts of dichloromethane, 37 parts of light calcium carbonate, 2640.5 parts of antioxidant BHT, 0.2 part of fumed silica, 0.8 part of white carbon black and 1 part of anatase titanium dioxide.
The preparation method of the novel environment-friendly adhesive comprises the following steps:
(1) placing styrene-isoprene-styrene block copolymer and poly α -methylstyrene resin into an internal mixer with the temperature of 130 ℃ for melting and mixing for 5min, and extruding and molding to prepare particles;
(2) adding toluene, methyl acetate, No. 120 solvent oil and dichloromethane into a reaction vessel, adding C9 petroleum resin, chlorinated polypropylene resin and antioxidant BHT264 under the condition of stirring, and stirring until the materials are uniformly dissolved;
(3) adding the particles prepared in the step (1) under the stirring condition, and stirring until the particles are uniformly dissolved;
(4) adding light calcium carbonate, fumed silica, white carbon black and anatase titanium dioxide, stirring until the mixture is uniformly mixed, and discharging to obtain the calcium carbonate-titanium dioxide-titanium white pigment composite.
Example 5
The novel environment-friendly adhesive comprises the following components, by weight, 16 parts of a styrene-isoprene-styrene segmented copolymer, 10 parts of poly α -methylstyrene resin, 11.5 parts of C9 petroleum resin, 4 parts of toluene, 10 parts of methyl acetate, 9 parts of 120# solvent oil, 2 parts of dichloromethane, 35 parts of light calcium carbonate, 2640.5 parts of an antioxidant BHT, 0.2 part of organic bentonite, 0.8 part of carbon black and 1 part of anatase titanium dioxide.
The preparation method of the novel environment-friendly adhesive comprises the following steps:
(1) melting and mixing styrene-isoprene-styrene block copolymer and poly α -methylstyrene resin in an internal mixer at 130 deg.C for 5min, extruding, and granulating
(2) Adding toluene, methyl acetate, 120# solvent oil and dichloromethane into a reaction vessel, adding C9 petroleum resin and antioxidant BHT264 under the condition of stirring, and stirring until the mixture is dissolved uniformly;
(3) adding the particles prepared in the step (1) under the stirring condition, and stirring until the particles are uniformly dissolved;
(4) adding light calcium carbonate, organic bentonite, carbon black and anatase titanium dioxide, stirring until the mixture is uniformly mixed, and discharging to obtain the calcium carbonate.
Examples of the experiments
The basic properties of each of the novel environmentally friendly adhesives of examples 1-5, including tensile strength, shear strength, and mold resistance rating, were tested according to the GB/T14683-2003 and GB/T1741-2007, and the results are shown in Table 1.
TABLE 1 basic Properties of novel environmentally friendly Adhesives
Note: test conditions for shear strength: test at 23 ℃ after 48h of bonding, test materials: wood-wood.
As can be seen from the above table, the tensile strength and the shear strength of the novel environment-friendly adhesive meet the national standard, and the novel environment-friendly adhesive disclosed by the invention can be simultaneously applied to the fields of structural sealing and bonding. In addition, the mildew-proof grade in the fields of structural sealing and bonding reaches the highest standard of grade 0, which shows that the novel environment-friendly adhesive disclosed by the invention has excellent mildew-proof performance, can be applied to a humid environment, and does not influence the attractiveness of a product and the service life of the adhesive.
Claims (8)
1. The environment-friendly adhesive is characterized by comprising the following components in parts by weight:
the thermoplastic elastomer is a phenylethane-isoprene-styrene segmented copolymer;
the tackifying resin is one or a mixture of chlorinated polypropylene resin and C9 petroleum resin;
the granular powder is one or a mixture of more of light calcium carbonate, barium sulfate, talcum powder, mica powder and kaolin;
the solvent is one or a mixture of more of cyclohexane, methyl acetate, ethyl acetate, dimethyl carbonate, No. 120 solvent oil, No. 6 solvent oil, acetone, toluene and dichloromethane;
the thixotropic agent is one of organic bentonite, fumed silica, metal soap and hydrogenated castor oil.
2. The environment-friendly adhesive as claimed in claim 1, wherein the solvent is toluene, 120# solvent oil, methyl acetate and dichloromethane in a mass ratio of 0.1-0.25: 0.2-0.5: 0.25-0.4: 0-0.1 of a mixture.
3. The environment-friendly adhesive according to claim 1, wherein the antioxidant is one of a compound or a composite oxidant of an aromatic amine antioxidant, a hindered phenol antioxidant, a thiodipropionic acid diester antioxidant and a phosphite antioxidant.
4. The environment-friendly adhesive as claimed in claim 1, wherein the reinforcing agent is one of carbon black, white carbon black, silicate, activated calcium carbonate and zinc oxide.
5. The environment-friendly adhesive as claimed in claim 1, wherein the titanium dioxide is one or more of rutile type titanium dioxide, anatase type titanium dioxide and brookite type titanium dioxide.
6. The preparation method of the environment-friendly adhesive as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) putting the thermoplastic elastomer and the poly α -methyl styrene resin into an internal mixer together, melting and mixing for 3-8 minutes, extruding and molding to prepare particles;
(2) adding a solvent into a reaction vessel, adding tackifying resin and an antioxidant under the stirring condition, and stirring until the tackifying resin and the antioxidant are dissolved uniformly;
(3) adding the particles prepared in the step (1) under the stirring condition, and stirring until the particles are uniformly dissolved;
(4) and adding granular powder, a reinforcing agent, a thixotropic agent and titanium dioxide, stirring until the mixture is uniformly mixed, and discharging to obtain the novel environment-friendly adhesive.
7. The method for preparing environment-friendly adhesive according to claim 6, wherein the temperature of the internal mixer is 130-180 ℃.
8. The application of the environment-friendly adhesive as defined in any one of claims 1-5, wherein the environment-friendly adhesive can be applied to the fields of structural sealing and bonding at the same time.
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| CN111793457A (en) * | 2019-04-09 | 2020-10-20 | 安徽米兰士装饰材料有限公司 | Novel environment-friendly smashing-free brick toughening film waterproof adhesive and preparation method thereof |
| CN112409955A (en) * | 2019-08-20 | 2021-02-26 | 广东顺德三和化工有限公司 | Nail-free glue and preparation method thereof |
| CN110903711A (en) * | 2019-11-29 | 2020-03-24 | 东来涂料技术（上海）股份有限公司 | Chlorinated polypropylene coating and preparation method thereof |
| JP7414505B2 (en) * | 2019-12-13 | 2024-01-16 | ヘンケルジャパン株式会社 | Alkaline dispersion hot melt adhesive |
| CN113278393B (en) * | 2021-04-02 | 2022-12-09 | 江门保实捷化工有限公司 | Heat-resistant PP hot melt adhesive and preparation method and application thereof |
| CN117106394A (en) * | 2023-02-27 | 2023-11-24 | 重庆中润新材料股份有限公司 | Ultraviolet light curing adhesive for bonding membrane electrode of hydrogen fuel cell |
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| US5403658A (en) * | 1994-04-15 | 1995-04-04 | Shell Oil Company | Adhesives containing vinyl aromatic hydrocarbon/diene/acrylic monomer block copolymers |
| US20070231571A1 (en) * | 2006-04-04 | 2007-10-04 | Richard Lane | Pressure sensitive adhesive (PSA) laminates |
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| CN103484043A (en) * | 2013-09-22 | 2014-01-01 | 抚顺哥俩好化学有限公司 | Environment-friendly and decorative nail-free glue and preparation method thereof |
| CN105255414A (en) * | 2015-11-25 | 2016-01-20 | 成都锦汇科技有限公司 | Environment-friendly adhesive and preparation method thereof |
| CN106753093A (en) * | 2016-12-23 | 2017-05-31 | 上海康达新能源材料有限公司 | A kind of aerosol photopolymer coating and preparation method thereof |
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