CN111978530A - Low-viscosity high-cost-performance polyester acrylate and preparation method thereof - Google Patents
Low-viscosity high-cost-performance polyester acrylate and preparation method thereof Download PDFInfo
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- CN111978530A CN111978530A CN202010899675.XA CN202010899675A CN111978530A CN 111978530 A CN111978530 A CN 111978530A CN 202010899675 A CN202010899675 A CN 202010899675A CN 111978530 A CN111978530 A CN 111978530A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The application discloses a low-viscosity high-cost performance polyester acrylate and a preparation method thereof. The invention obtains the best raw material composition and proportion through a large number of experimental screens, and optimizes the best synthesis process through a large number of experiments. The prepared low-viscosity high-cost performance polyester acrylate has the outstanding advantages of low viscosity, high cost performance, good hardness, certain flexibility, high curing speed and the like.
Description
Technical Field
The invention relates to an oligomer for a photocureable coating, in particular to a low-viscosity high-cost-performance polyester acrylate and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
Ultraviolet (UV) curing technology is a new coating technology starting at the end of the last 60 s of the century. The technology is mainly characterized in that oligomers (light-cured resin and light-cured monomer) and a photoinitiator are subjected to light cross-linking reaction under the irradiation of ultraviolet light to be cured into a target product. The UV curing technology is gradually a mainstream curing technology under the development trend of higher and higher environmental protection requirements in recent years due to the outstanding advantages of fast curing, low energy consumption, low pollution, excellent performance and the like.
Polyester acrylate (PEA) resin is an indispensable photocuring resin in the field of Ultraviolet (UV) curing, and is mainly obtained by esterification reaction of various organic alcohols, organic acids or organic acid anhydrides and acrylic monomers under the action of a catalyst. Owing to the diversity of the used raw materials and the designability of the structure, the PEA resin and the cured film have wide controllability in various final properties, and are widely applied to the fields of coatings, printing ink, adhesives and the like.
At present, due to the increasing domestic environmental protection pressure, the low-viscosity light-cured resin which can be used for solvent-free spraying is more and more popular among the technical workers. Although the viscosity of the current PEA system is lower and the price is not high, the PEA system with lower viscosity, higher cost performance and better performance is still less, and in order to solve the problems, the polyester acrylate with low viscosity and high cost performance and the preparation method thereof are provided, so that the viscosity and the price of the resin are reduced, and the better resin stability and the better mechanical performance of a cured film are ensured.
Chinese patent CN201010280182.4 discloses a flexible package composite film ultraviolet light curing water-based adhesive and a preparation method thereof, wherein the water-based ultraviolet light curing resin is 32-58%, deionized water is 36-55%, a water-based wetting agent is 1.2-2.8%, a water-based defoaming agent is 0.5-1.4%, a water-based leveling agent is 1-3%, a thickening agent is 0.3-0.8%, a photoinitiator is 3-5%, 998-3012 parts of polyester dihydric alcohol, 68-303 parts of epoxy resin, 39-73 parts of rosin maleic anhydride, 250-351 parts of tricarboxylic acid, 202-237 parts of hydrophilic dihydric alcohol, 0.5-1.1 parts of stannous chloride, 1.3-3.2 parts of antioxidant, 0.5-1.6 parts of dibutyltin dilaurate, 39-71 parts of trimethylolpropane and 645-1150 parts of butanone, the polyester dihydric alcohol is selected from polybutylene adipate, polyethylene glycol, polycaprolactone glycol, One or more mixtures of poly (1, 6-hexanediol carbonate) glycol, but the prior art is slightly deficient in terms of low cost performance, high viscosity, and insufficient comprehensive performance.
Chinese patent CN200610049898.7 discloses a photo-curing water-based acrylic epoxy resin emulsion and a coating prepared from the same, which comprises a self-emulsifying acrylic epoxy emulsifier, styrene modified acrylic epoxy ester, a diluent, a photoinitiator and the balance of water, but the prior art is slightly deficient in the aspects of low cost performance, high viscosity, insufficient comprehensive performance and the like.
Chinese patent CN00117364.2 discloses a thermosetting weather-resistant low-gloss powder coating and a preparation method thereof, the powder coating mainly comprises linear carboxyl-terminated polyester resin and acrylic resin containing epoxy groups, various suitable fillers and auxiliaries are added, and the weather-resistant low-gloss powder coating is obtained by melting, mixing, cooling, crushing and sieving, but the prior art is slightly deficient in the aspects of low cost performance, high viscosity, insufficient comprehensive performance and the like.
Disclosure of Invention
The invention provides a low-viscosity high-cost performance polyester acrylate and a preparation method thereof, and solves the technical problems of low cost performance, high viscosity, insufficient comprehensive performance and the like of the conventional material.
The invention adopts the following technical scheme: the low-viscosity high-cost-performance polyester acrylate comprises the following raw materials in parts by mass: 10-50 parts of organic dihydric alcohol, 10-50 parts of organic acid anhydride or organic dicarboxylic acid, 5-50 parts of acrylic monomer, 1-20 parts of compound containing epoxy group, solvent, catalyst and polymerization inhibitor.
As a preferred technical scheme of the invention: the organic diol is one of diethylene glycol, saturated alkyl glycols with different molecular weights and structures, polyethylene glycol with different molecular weights, polypropylene glycol with different molecular weights or any combination thereof.
As a preferred technical scheme of the invention: the organic acid anhydride or the organic dicarboxylic acid is one of maleic anhydride, succinic anhydride, phthalic anhydride, sebacic anhydride, isophthalic acid, terephthalic acid, saturated dicarboxylic acids with different molecular weights and structures, unsaturated dicarboxylic acids with different molecular weights and structures, or any combination thereof.
As a preferred technical scheme of the invention: the acrylic monomer is one of acrylic acid and methacrylic acid or any combination thereof.
As a preferred technical scheme of the invention: the solvent is one of benzene, toluene, xylene and cyclohexane or any combination thereof.
As a preferred technical scheme of the invention: the compound containing the epoxy group is one or any combination of epoxy diluent, epoxy resin and epoxy chloropropane.
As a preferred technical scheme of the invention: the catalyst is p-toluenesulfonic acid and/or methanesulfonic acid.
As a preferred technical scheme of the invention: the polymerization inhibitor is p-hydroxyanisole and hydroquinone.
A method for preparing the low-viscosity high-cost-performance polyester acrylate comprises the following steps:
the first step is as follows: weighing organic dihydric alcohol, organic acid anhydride or organic dicarboxylic acid, acrylic monomers, epoxy group-containing compounds, solvents, polymerization inhibitors and catalysts according to the mass part ratio;
step two, synthesizing a hydroxyl-terminated intermediate: reacting organic dihydric alcohol, organic acid anhydride or organic dicarboxylic acid, 0.4-1.5 parts of catalyst p-toluenesulfonic acid and 5-30 parts of solvent at the reaction temperature of 130-;
the third step: reacting a hydroxyl-terminated intermediate, an acrylic monomer, 0.5-2% of methanesulfonic acid serving as a catalyst, 0.2-1 part of p-hydroxyanisole serving as a polymerization inhibitor, 0.05-0.5 part of hydroquinone, 10-50 parts of a solvent, 50-200ml of system air flow rate/(min & 1000g of material), 100-140 ℃ of reaction temperature and 6-12 hours of reaction time to obtain a semi-finished product;
the fourth step: removing the solvent from the semi-finished product by reduced pressure distillation;
the fifth step: finally, an epoxy group-containing compound is added to reduce the acid value to be less than or equal to 8mgKOH/g, and the low-viscosity high-cost performance polyester acrylate is prepared.
Advantageous effects
Compared with the prior art, the low-viscosity high-cost-performance polyester acrylate and the preparation method thereof have the following technical effects:
1. the viscosity of the low-viscosity high-cost performance polyester acrylate is lower than that of the common polyester acrylate and has higher cost performance;
2. the storage stability is excellent.
3. The paint film obtained by UV curing has the advantages of high curing speed, good hardness and certain flexibility, and has better application prospects in the fields of woodware, plastic, printing ink and the like.
4. The resin with lower viscosity is obtained while ensuring the excellent basic performance of the resin by using and proportioning adjustment of common raw materials in the industry, and is beneficial to developing common problems which need to be solved urgently in industries such as solvent-free spraying and high use cost of the resin.
Detailed Description
The present invention is further described with reference to the following examples, which are intended to be illustrative only and not to be limiting of the scope of the claims, and other alternatives which may occur to those skilled in the art are within the scope of the claims.
Example 1:
the preparation method of the low-viscosity high-cost performance polyester acrylate comprises the following steps:
the first step is as follows: 178g of diethylene glycol, 132.8g of terephthalic acid, 92.8g of fumaric acid, 2g of p-toluenesulfonic acid and 60g of toluene are put into a 1L four-neck flask at one time, the temperature of the system is slowly increased to 120 ℃ to obtain liquid, the temperature is slowly controlled to 160 ℃, the temperature is kept for 10 hours, the medium acid value is controlled to be less than or equal to 5mgKOH/g, an intermediate is prepared, and the temperature is reduced to prepare two-step reaction.
The second step is that: adding 104.8g of acrylic acid, 1g of methanesulfonic acid, 0.6g of p-hydroxyanisole, 0.2g of hydroquinone and 200g of toluene into the first step of reaction after cooling, controlling the air flow rate to be 100ml/min before heating, then slowly controlling the temperature to be 115 ℃ to discharge liquid, preserving the temperature for 8 hours, controlling the acid value to be less than or equal to 15mgKOH/g, removing the solvent, reacting with 17g of epoxy chloropropane until the acid value is less than or equal to 8mgKOH/g, and performing vacuum degassing to obtain the finished product of the low-viscosity high-cost-performance polyester acrylate.
Example 2:
the preparation method of the low-viscosity high-cost performance polyester acrylate comprises the following steps:
firstly, 70.6g of diethylene glycol, 161.7g of neopentyl glycol, 106.8g of phthalic anhydride, 38.1g of maleic anhydride, 3.5g of p-toluenesulfonic acid and 45g of toluene are put into a 1L four-neck flask at one time, the temperature of the system is slowly increased to 115 ℃ to obtain liquid, then the temperature is slowly controlled to 130 ℃, the temperature is kept for 12 hours, the medium acid value is controlled to be less than or equal to 5mgKOH/g, an intermediate is prepared, and the temperature is reduced to prepare two-step reaction.
And secondly, putting 173.3g of methacrylic acid, 1g of methanesulfonic acid, 0.8g of p-hydroxyanisole, 0.4g of hydroquinone and 220g of cyclohexane into the first step of reaction after cooling, controlling the air flow rate to be 70ml/min before heating, then slowly controlling the temperature to 120 ℃ to discharge liquid, keeping the temperature for 6 hours, controlling the acid value to be less than or equal to 12mgKOH/g, removing the solvent, and then reacting with 15g of 1, 4-butanediol diglycidyl ether until the acid value is less than or equal to 6mgKOH/g to obtain the finished product of the low-viscosity high-cost-performance polyester acrylate.
Comparative example 1:
the preparation method of the low-viscosity high-cost performance polyester acrylate comprises the following steps:
the first step is as follows: firstly, 212g of diethylene glycol, 166g of terephthalic acid, 2g of p-toluenesulfonic acid and 60g of toluene are put into a 1L four-neck flask at one time, the temperature of the system is slowly increased to 120 ℃ to obtain liquid, then the temperature is slowly controlled to 160 ℃, the temperature is kept for 10 hours, the central control acid value is less than or equal to 5mgKOH/g, an intermediate is prepared, and the temperature is reduced to prepare the two-step reaction.
The second step is that: adding 150g of acrylic acid, 1g of methanesulfonic acid, 0.6g of p-hydroxyanisole, 0.2g of hydroquinone and 200g of toluene into the first step of reaction after cooling, controlling the air flow rate to be 100ml/min before heating, then slowly controlling the temperature to be 115 ℃ to obtain liquid, keeping the temperature for 8h, controlling the acid value to be less than or equal to 15mgKOH/g, removing the solvent, reacting with 17g of epoxy chloropropane until the acid value is less than or equal to 8mgKOH/g, and performing vacuum degassing to obtain the finished product of the low-viscosity high-cost-performance polyester acrylate.
TABLE 1 Performance test results
Note: the curing speed in the table is 80mW/cm directly on a UV curing machine2The light intensity curing test of (2) was conducted, and the storage stability was measured after 3 days of storage at 80 ℃.
The experiment results show that a paint film obtained by UV curing the low-viscosity high-cost performance polyester acrylate prepared by the invention has high wear resistance, high hardness, chemical resistance and excellent curing speed.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The low-viscosity high-cost-performance polyester acrylate is characterized by comprising the following raw materials in parts by mass: 10-50 parts of organic dihydric alcohol, 10-50 parts of organic acid anhydride or organic dicarboxylic acid, 5-50 parts of acrylic monomer, 1-20 parts of compound containing epoxy group, solvent, catalyst and polymerization inhibitor.
2. A low viscosity cost-effective polyester acrylate according to claim 1 wherein: the organic diol is one of diethylene glycol, saturated alkyl glycols with different molecular weights and structures, polyethylene glycol with different molecular weights, polypropylene glycol with different molecular weights or any combination thereof.
3. A low viscosity cost-effective polyester acrylate according to claim 1 wherein: the organic acid anhydride or the organic dicarboxylic acid is one of maleic anhydride, succinic anhydride, phthalic anhydride, sebacic anhydride, isophthalic acid, terephthalic acid, saturated dicarboxylic acids with different molecular weights and structures, unsaturated dicarboxylic acids with different molecular weights and structures, or any combination thereof.
4. A low viscosity cost-effective polyester acrylate according to claim 1 wherein: the acrylic monomer is one of acrylic acid and methacrylic acid or any combination thereof.
5. A low viscosity cost-effective polyester acrylate according to claim 1 wherein: the solvent is one of benzene, toluene, xylene and cyclohexane or any combination thereof.
6. A low viscosity cost-effective polyester acrylate according to claim 1 wherein: the compound containing the epoxy group is one or any combination of epoxy diluent, epoxy resin and epoxy chloropropane.
7. A low viscosity cost-effective polyester acrylate according to claim 1 wherein: the catalyst is p-toluenesulfonic acid and/or methanesulfonic acid.
8. A low viscosity cost-effective polyester acrylate according to claim 1 wherein: the polymerization inhibitor is p-hydroxyanisole and hydroquinone.
9. A method for preparing the low-viscosity cost-effective polyester acrylate of any one of claims 1 to 8, comprising the steps of:
the first step is as follows: weighing organic dihydric alcohol, organic acid anhydride or organic dicarboxylic acid, acrylic monomers, epoxy group-containing compounds, solvents, polymerization inhibitors and catalysts according to the mass part ratio;
step two, synthesizing a hydroxyl-terminated intermediate: reacting organic dihydric alcohol, organic acid anhydride or organic dicarboxylic acid, 0.4-1.5 parts of catalyst p-toluenesulfonic acid and 5-30 parts of solvent at the reaction temperature of 130-;
the third step: reacting a hydroxyl-terminated intermediate, an acrylic monomer, 0.5-2% of methanesulfonic acid serving as a catalyst, 0.2-1 part of p-hydroxyanisole serving as a polymerization inhibitor, 0.05-0.5 part of hydroquinone, 10-50 parts of a solvent, 50-200ml of system air flow rate/(min & 1000g of material), 100-140 ℃ of reaction temperature and 6-12 hours of reaction time to obtain a semi-finished product;
the fourth step: removing the solvent from the semi-finished product by reduced pressure distillation;
the fifth step: finally, an epoxy group-containing compound is added to reduce the acid value to be less than or equal to 8mgKOH/g, and the low-viscosity high-cost performance polyester acrylate is prepared.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010899675.XA CN111978530A (en) | 2020-08-31 | 2020-08-31 | Low-viscosity high-cost-performance polyester acrylate and preparation method thereof |
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| CN202010899675.XA CN111978530A (en) | 2020-08-31 | 2020-08-31 | Low-viscosity high-cost-performance polyester acrylate and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717618A (en) * | 2021-09-01 | 2021-11-30 | 青岛科技大学 | Photocuring coating and preparation method thereof |
| CN114891190A (en) * | 2022-05-07 | 2022-08-12 | 上海立邦长润发涂料有限公司 | Ultraviolet-curable low-viscosity polyester and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254862A (en) * | 2015-10-20 | 2016-01-20 | 三棵树涂料股份有限公司 | Rapidly cured UV (ultraviolet) polyester acrylate with high scratch resistance and preparation method of UV polyester acrylate |
| CN107880258A (en) * | 2017-10-16 | 2018-04-06 | 广州五行材料科技有限公司 | Low viscosity modified polyester acrylate ester and preparation method thereof |
| CN110105851A (en) * | 2019-04-28 | 2019-08-09 | 英德市雅家涂料有限公司 | A kind of quick-setting UV polyester acrylate of low viscosity and its preparation process |
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2020
- 2020-08-31 CN CN202010899675.XA patent/CN111978530A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254862A (en) * | 2015-10-20 | 2016-01-20 | 三棵树涂料股份有限公司 | Rapidly cured UV (ultraviolet) polyester acrylate with high scratch resistance and preparation method of UV polyester acrylate |
| CN107880258A (en) * | 2017-10-16 | 2018-04-06 | 广州五行材料科技有限公司 | Low viscosity modified polyester acrylate ester and preparation method thereof |
| CN110105851A (en) * | 2019-04-28 | 2019-08-09 | 英德市雅家涂料有限公司 | A kind of quick-setting UV polyester acrylate of low viscosity and its preparation process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717618A (en) * | 2021-09-01 | 2021-11-30 | 青岛科技大学 | Photocuring coating and preparation method thereof |
| CN114891190A (en) * | 2022-05-07 | 2022-08-12 | 上海立邦长润发涂料有限公司 | Ultraviolet-curable low-viscosity polyester and preparation method thereof |
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Application publication date: 20201124 |