CN104003874B - A kind of 4 functionality aliphatic epoxy acrylate newly and preparation method thereof and application - Google Patents
A kind of 4 functionality aliphatic epoxy acrylate newly and preparation method thereof and application Download PDFInfo
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- CN104003874B CN104003874B CN201410172932.4A CN201410172932A CN104003874B CN 104003874 B CN104003874 B CN 104003874B CN 201410172932 A CN201410172932 A CN 201410172932A CN 104003874 B CN104003874 B CN 104003874B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to Material Field, relate to a kind of 4 functionality aliphatic epoxy acrylate newly and preparation method thereof and application.First under catalyzer, stopper effect, react the obtained 1 functionality acrylate intermediate (I) containing 1 carboxyl by Succinic anhydried with (methyl) vinylformic acid hydroxyl second (third) ester, intermediate (I) and tetramethylolmethane glycidyl ether be obtained 4 functionality aliphatic epoxy acrylate under the effect of catalyzer, stopper.After 4 functionality UV photocuring aliphatic epoxy acrylate solidifications prepared by the present invention, have that hardness is high, wear-resisting, scratch resistance, heat-resisting, weathering resistance etc. be excellent, can apply at the raw material as UV coating, ink, tackiness agent.
Description
Technical field
The invention belongs to Material Field, relate to a kind of 4 functionality aliphatic epoxy acrylate and preparation method thereof and application.
Background technology
Along with developing rapidly and the strict restriction of legislations of environmental protection to solvent of science and technology, UV photocuring macromolecular material is more and more subject to people's attention.UV photo-curing material have quick solidifying, energy consumption low, pollute less, the premium properties such as efficiency is high, be thus widely used in the fields such as coating, printing and electronic industry, development in recent years is rapid.Epoxy acrylate (epoxyacrylate, EA) be obtained through esterification by ring opening by the compound and acrylic or methacrylic acid that contain epoxide group, it is a kind of important Photocurable oligomers, there is the premium propertiess such as low stimulation, curing speed is fast, high transparent, hardness are high, be widely used in the fields such as light-curable ink, coating, tackiness agent, be widely used at the U.S., Japan, countries in Europe.In recent years, along with UV-curing technology is in the rise of China, novel photo-curing material is more and more wider as the raw material purposes of UV coating, ink, tackiness agent, and usage quantity is increasing year by year.
Summary of the invention
The object of the invention is the above-mentioned deficiency for prior art, a kind of 4 functionality aliphatic epoxy acrylate are provided.
Another object of the present invention is to provide the preparation method of this 4 functionality aliphatic epoxy acrylate.
Another object of the present invention is to provide the application of this 4 functionality aliphatic epoxy acrylate.
Object of the present invention realizes by following technical scheme:
A kind of 4 functionality aliphatic epoxy acrylate, prepare by the following method: first by Succinic anhydried (CASNO.108-30-5, Chinese another name: succinyl oxide, molecular formula: C
4h
4o
3molecular weight 100.07) under catalyzer, stopper effect, react the obtained 1 functionality acrylate intermediate (I) containing 1 carboxyl with (methyl) vinylformic acid hydroxyl second (third) ester, intermediate (I) and tetramethylolmethane glycidyl ether (CAS:3126-63-4, molecular formula: C
17h
28o
8, molecular weight: 360.3994) obtained 4 functionality aliphatic epoxy acrylate (aliphatic epoxy four acrylic acid ester) under the effect of catalyzer, stopper.Described (methyl) vinylformic acid hydroxyl second (third) ester be selected from hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate or Propylene glycol monoacrylate any one.
Wherein,
For Hydroxyethyl acrylate, the first step reaction formula is:
The 1 functionality acrylate intermediate (I) containing 1 carboxyl is prepared preferably by following steps: (methyl) vinylformic acid hydroxyl second (third) ester and Succinic anhydried are under catalyst action, in a kettle. in 60 DEG C-120 DEG C reaction 1-6 hour, then less than 50 DEG C are cooled to, the obtained 1 functionality acrylate intermediate (I) containing 1 carboxyl; Wherein, preferred 1:(0.8 ~ 1.5 of mol ratio of (methyl) vinylformic acid hydroxyl second (third) ester and Succinic anhydried).Under the conditions of the reaction according to the invention, Succinic anhydried open loop generates 1 carboxyl, and when reaction system acid number drops to constant, namely Succinic anhydried carries out ring-opening reaction generation carboxyl completely, and transformation efficiency is more than 99.9%.
One or both or two or more arbitrary proportion miscellany in described the first step catalysts preferred Louis bases, quaternary ammonium salt, quaternary phosphine salt; Preferred from triethylamine, N further, one or both or two or more arbitrary proportion miscellany in N-dimethyl benzylamine, N, N-diethyl benzylamine, triphenyl phosphorus, tributyl phosphorus, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, 4 bromide, tetraethylammonium bromide, Tetrabutyl amonium bromide, tri-phenyl-ethyl phosphonium bromide, four butyl phosphonium bromides; Catalyst levels is the 0.1wt%-2wt% of (methyl) vinylformic acid hydroxyl second (third) ester and Succinic anhydried total mass.The preferred MEHQ of stopper or Resorcinol, its consumption is 100-5000ppm.
Second step reaction formula:
4 described functionality aliphatic epoxy acrylate are prepared preferably by following steps: tetramethylolmethane glycidyl ether and the obtained 1 functionality acrylate intermediate (I) containing 1 carboxyl, under catalyzer, stopper effect, obtain 4 described functionality aliphatic epoxy acrylate in 60 DEG C-120 DEG C reactions 1-10 hour; Wherein, described tetramethylolmethane glycidyl ether and the mol ratio of Succinic anhydried are (0.22 ~ 0.3): 1.
4 described functionality aliphatic epoxy acrylate are prepared preferably by following steps further: tetramethylolmethane glycidyl ether and the obtained 1 functionality acrylate intermediate (I) containing 1 carboxyl, under catalyzer, stopper effect, obtain 4 described functionality aliphatic epoxy acrylate in 70 DEG C-110 DEG C reactions 3-9 hour; Wherein, described tetramethylolmethane glycidyl ether and the mol ratio of Succinic anhydried are (0.24 ~ 0.27): 1.
Wherein stopper can be MEHQ or Resorcinol, and its consumption is 100-5000ppm.
Described second step catalysts is triethylamine, N, N-dimethyl benzylamine, N, N-diethyl benzylamine, triphenyl phosphorus, Louis's bases such as tributyl phosphorus, or benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, 4 bromide, tetraethylammonium bromide, the quaternary ammonium salts such as Tetrabutyl amonium bromide, or tri-phenyl-ethyl phosphonium bromide, one or both or two or more arbitrary proportion miscellany in the quaternary phosphine salts such as four butyl phosphonium bromides, catalyst levels is the 0.1wt%-2wt% of tetramethylolmethane glycidyl ether and intermediate (I) total mass.
Without the need to carrying out purifying to intermediate after the first step reaction terminating, directly adding tetramethylolmethane glycidyl ether, and adding catalyzer and stopper reacts.Wherein, the first step reaction amount that adds catalyzer with the total mass of reactant Succinic anhydried and (methyl) vinylformic acid hydroxyl second (third) ester for benchmark; The amount of second step catalysts (comprising the amount of the catalyzer added when the first step reacts the catalyzer and second step reaction that add) with the total mass of reactant Succinic anhydried, (methyl) vinylformic acid hydroxyl second (third) ester and tetramethylolmethane glycidyl ether for benchmark.In the first step reaction, the stopper that adds is also the same with catalyzer, will enter into second reaction and play a role, and the consumption that second step reacts stopper is the amount sum that the first step reacts the stopper that the add-on of stopper and second step are added.
The application of 4 functionality aliphatic epoxy acrylate of the present invention in preparation UV coating, ink or tackiness agent.
Beneficial effect:
The present invention discloses a kind of 4 functionality UV photocuring aliphatic epoxy acrylate newly and preparation method thereof.After the solidification of this 4 functionality UV photocuring aliphatic epoxy acrylate, have that hardness is high, wear-resisting, scratch resistance, heat-resisting, weathering resistance etc. be excellent, can apply at the raw material as UV coating, ink, tackiness agent.
Embodiment
Embodiment 1:
The first step, drops into 2000 grams of Succinic anhydrieds (CASNO.108-30-5, molecular formula: C in 8L reactor
4h
4o
3, molecular weight 100.07), 15 grams of benzyltriethylammoinium chlorides, 1.5 grams of MEHQ, 2420 grams of Hydroxyethyl acrylates (CASNo.:818 ?61 ?1, molecular formula: C
5h
8o
3molecular weight 116.12, content is by 96%), start stirring, be warming up to 70 DEG C, be incubated 1 hour, be warmed up to 80 DEG C of insulations 1 hour again, then be warming up to 100 DEG C of insulations 3 hours, react constant to acid number, then less than 50 DEG C are cooled to, obtained 4436.5 grams, the 1 functionality acrylate intermediate (I) containing 1 carboxyl.Without the need to carrying out separation and purification, directly carry out second step reaction.
Second step, then drops into 1800 grams of tetramethylolmethane glycidyl ethers ((CAS:3126-63-4, molecular formula: C in 8L reactor
17h
28o
8360.3994), 5 grams of benzyltriethylammoinium chlorides, 1 gram of MEHQ molecular weight:, be warming up to 70 DEG C, be incubated 1 hour, be warmed up to 80 DEG C of insulations 1 hour again, be warmed up to 90 DEG C of insulations 1 hour again, be warming up to 100 DEG C of insulations 1 hour again, be warming up to 110 DEG C of insulations 5 hours again, react constant to acid number, then be cooled to 50 DEG C and obtain crude product with bottom discharge, overanxious through 200 mesh filter screens (gauze), obtain 6117 grams of clear thick liquid 4 functionality aliphatic epoxy acrylate (aliphatic epoxy four acrylic acid ester) C
53h
76o
32, structure is such as formula shown in (II).
1HNMR(400MHz,CD
3OD,δppm)：2.84‐2.86(16H,m,4CH
2CH
2),3.40(4H,m,4CH
2),3.58(4H,brs,4OH),3.65(4H,m,4CH
2),4.11(4H,m,4CH
2),4.14(4H,m,4CH),4.31‐4.38(20H,m,4CH
2,4CH
2CH
2),5.59(4H,d,4CH＝CH
2),5.80(8H,s,4CH
2),6.05(4H,m,4CH＝CH
2),6.27(4H,m,4CH＝CH
2)
13CNMR(100MHz,CD
3OD,δppm)：29.5(8CH
2),44.8(1C),61.8(4CH
2),62.2(4CH
2),65.5(4CH
2),68.7(4CH),71.0(4CH
2),73.6(4CH
2),128.2(4CH),131.3(4CH
2),166.5(4CO),173.1(8CO)
Embodiment 2:
The first step, drops into 2000 grams of Succinic anhydrieds (CASNO.108-30-5, molecular formula: C in 8L reactor
4h
4o
3, molecular weight 100.07), 10 grams of benzyltriethylammoinium chlorides, 5 grams of tetramethyl ammonium chlorides, 1.5 grams of MEHQ, 2425 grams of Hydroxyethyl acrylates (CASNo.:818 ?61 ?1, molecular formula: C
4h
4o
3, molecular weight 116.12, content is by 96%), start stirring, be warming up to 70 DEG C, be incubated 1 hour, then be warmed up to 80 DEG C of insulations 1 hour, be warming up to 100 DEG C of insulations 3 hours again, react constant to acid number, be then cooled to less than 50 DEG C, obtained 4441.5 grams, the 1 functionality acrylate intermediate (I) containing 1 carboxyl.Without the need to carrying out separation and purification, directly carry out second step reaction.
Second step, then drops into 1800 grams of tetramethylolmethane glycidyl ethers (CAS:3126-63-4, molecular formula: C in 8L reactor
17h
28o
8360.3994), 6.5 grams of triethylamines, 1 gram of Resorcinol molecular weight:, be warming up to 70 DEG C, be incubated 1 hour, be warmed up to 80 DEG C of insulations 1 hour again, be warmed up to 90 DEG C of insulations 1 hour again, be warming up to 100 DEG C of insulations 1 hour again, be warming up to 110 DEG C of insulations 5 hours again, react constant to acid number, then be cooled to 50 DEG C and obtain crude product with bottom discharge, overanxious through 200 mesh filter screens (gauze), obtain 6124 grams of clear thick liquid 4 functionality aliphatic epoxy acrylate (aliphatic epoxy four acrylic acid ester) C
53h
76o
32, structure is such as formula shown in (II).
Embodiment 3
Starting material
UV resin: 4 functionality aliphatic epoxy acrylate prepared by embodiment 1; 3 functionality aliphatic urethane acrylates (F5301, profit field, Jiangsu science and technology).
UV monomer: ditrimethylolpropane tetraacrylate (Di-TMPTA, profit field, Jiangsu); 1,6 hexanediol diacrylate (HDDA, profit field, Jiangsu); Isobornyl acrylate (IBOA, profit field, Jiangsu).
Light trigger: 1173, Nanjing Wa Li Chemical Industry Science Co., Ltd.
Auxiliary agent: Tego432, Tego92, German enlightening is high.
Mixed solvent: N-BUTYL ACETATE, toluene, mibk are 1:1:1 mixing in mass ratio.
Instrument and equipment
LT-1002 type uv cure machine, blue sky Te Deng Development Co., Ltd; QFZ type paint film adhesion determinator, Tianjin Ke Lian material-testing machine factory; RCA paper tape wear resistant instrument, Shanghai modern environment project institute; Water-bath; Cold cycling equipment.The preparation of coating
Take the UV resin of certain mass, then add UV monomer, light trigger, auxiliary agent, stir, be mixed with coating.The proportioning of coating is in Table l.
Table 1: the proportioning of coating
The preparation of film and solidification
Select the ABS plastic sheet material of 10cm × 10cm, first at its surface spraying one deck thermoplastic acrylic resin white primer, 60 DEG C of baking 3h, again at its surface spraying UV finish paint, coating thickness is about 20 μm, and photo solidification machine solidifies, and makes cured film reach surface drying, touch dry method with finger to characterize, record set time.
Performance test
Set time: experiment adopts finger to touch dry method, touching coating surface, being clamminess if do not felt, namely think that coating surface solidifies to point.
Pencil hardness: measure with reference to GB6739-86 film pencil hardness method.
Sticking power: measure with reference to GB/T1720-88 film adhesive assay method.Be divided into 7 grades, 1 grade of the best, 7 grades the poorest.
Wear resistance: RCA tests, 175g, 500 ± 50 times.
Water boiling resistance: with reference to standard GB/T/T1733 " paint film water tolerance assay method ".
Cold-hot circulates:
(1) scope and explanation: plastic paint because of moisture and hot ageing or losses of plasticizer, or there will be the trend of cracking when both have concurrently, adopts and is alternately exposed in climate cabinet and refrigerated tank the degree that can measure paint film and whether ftracture and ftracture.
(2) instrument: 1. damp heat box, 2. refrigerated tank, 3. color measurement instrument, 4. draws lattice device.
(3) measuring method: 1. test piece is put into relative temperature 100%, temperature is the hot case 24h of incubator of 38 DEG C.The placement of model should become 0-30 degree angle with vertical direction, and requires that plate plate is not in contact with each other mutually in process of the test.2., after 24h, immediately model is moved to 20h in the refrigerated tank of (-23 ± 1.5) DEG C, transfer time at most should more than 30S.3. take out model, at room temperature place 4h, 48h is a circulation so altogether, and period can carry out stage evaluation.4. carry out 15 circulations altogether, then model outward appearance, color, sticking power are tested.
(4) result represents: film should without cracking, variable color, loss of adhesion or other defect.
(5) reference standard: USS AAMA615-02 " on plastic material the industry standard of high-performance organic coating, performance requriements and test method ".
(1)
Result and discussion, resin is on the impact of film performance
UV resin is the main body of UV coating, and its performance determines the salient features of the rear film of solidification substantially.This experiment employing 3 functionality aliphatic epoxy acrylate and 4 functionality aliphatic urethane acrylate resins form different ingredients, and various Ingredient Amount is in table 1, and film performance is in table 2.
Table 2:4 official's aliphatic epoxy acrylate and 3 official's aliphatic urethane acrylate different ratio are on the impact of coating property
Reference:
(1) Yu Yingying. the coatings industry method of inspection and instrument complete works. Beijing: Chemical Industry Press, 2007:525.
Attached light trigger 1173 illustrates:
Manufacturer: Nanjing Wa Li Chemical Industry Science Co., Ltd
Chemical name: 2-hydroxy-2-methyl-1-phenyl-1-acetone
English name: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one
CASNO：7473-98-5
Molecular formula: C10H12O
Molecular weight: 164.2
Chemical structural formula:
Technical indicator:
Outward appearance: colourless to light yellow transparent liquid
Purity: >=99.0%
Boiling point: 80-81 DEG C (degree Celsius)
Transmittance: 425nm >=99.0%; 500nm >=99.3%
Fugitive constituent :≤0.2%
Ash :≤0.10%
Application:
1173 are applicable to vinylformic acid photocuring varnish system, as the varnish etc. of timber, metal, paper, plastics etc.1173 special recommendations, in the UV-needing to stand chronic sun exposure and color inhibition is coating material solidified, because 1173 is liquid, are highly susceptible to blended, so be applicable to and the composite use of other light trigger, suggestion addition is 1-4%w/w.
Claims (3)
1. the preparation method of a functionality aliphatic epoxy acrylate, it is characterized in that comprising following steps: the first step is reacted: first by (methyl) vinylformic acid hydroxyl second (third) ester and Succinic anhydried under catalyzer and stopper effect, in a kettle. in 60 DEG C-120 DEG C reaction 1-6 hour, then less than 50 DEG C are cooled to, the obtained 1 functionality acrylate intermediate containing 1 carboxyl (
); Wherein, described (methyl) vinylformic acid hydroxyl second (third) ester and the mol ratio of Succinic anhydried are 1:(0.8 ~ 1.5); Second step reacts: 1 functionality acrylate intermediate that tetramethylolmethane glycidyl ether contains 1 carboxyl with described (
) under catalyzer and stopper effect, the obtained 4 described functionality aliphatic epoxy acrylate in 60 DEG C-120 DEG C reactions 1-10 hour; Wherein, described tetramethylolmethane glycidyl ether and the first step react the mol ratio of the Succinic anhydried added for (0.22 ~ 0.30): 1; Wherein, described (methyl) vinylformic acid hydroxyl second (third) ester be selected from hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate or Propylene glycol monoacrylate any one; Described catalyzer is selected from triethylamine, N, one or both or two or more arbitrary proportion miscellany in N-dimethyl benzylamine, N, N-diethyl benzylamine, triphenylphosphine, tributylphosphine, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, 4 bromide, tetraethylammonium bromide, Tetrabutyl amonium bromide, tri-phenyl-ethyl phosphonium bromide, four butyl phosphonium bromides.
2. the preparation method of 4 functionality aliphatic epoxy acrylate according to claim 1, it is characterized in that the first step reaction terminate after without the need to carry out intermediate (
) separation and purification, directly add tetramethylolmethane glycidyl ether, and add catalyzer and stopper carries out second step reaction.
3. the preparation method of 4 functionality aliphatic epoxy acrylate according to any one of claim 1 ~ 2, is characterized in that catalyst levels is the 0.1wt%-2wt% of reactant total mass; Described stopper is MEHQ or Resorcinol, and its consumption is 100-5000ppm.
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| CN105820063B (en) * | 2016-04-15 | 2017-11-17 | 江苏利田科技股份有限公司 | A kind of 4 degree of functionality urethane acrylates based on anhydrous citric acid and its preparation method and application |
| CN108395522B (en) * | 2018-03-29 | 2020-05-19 | 广州市嵩达新材料科技有限公司 | Epoxy acrylic resin with four functionalities and preparation method and application thereof |
| CN112175489B (en) * | 2020-09-04 | 2022-03-22 | 江苏利田科技股份有限公司 | Hybrid epoxy acrylate UV coating with high surface hardness |
| TWI781508B (en) * | 2020-10-30 | 2022-10-21 | 財團法人工業技術研究院 | Resin and ink |
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