CN109265649B

CN109265649B - Self-emulsifying radiation curing composition and preparation method thereof

Info

Publication number: CN109265649B
Application number: CN201710578904.6A
Authority: CN
Inventors: 宋小伟; 章学良; 刘松玲; 张攀; 李喜乐; 马天如; 黄剑莉; 许文然
Original assignee: Lucky Huaguang Graphics Co Ltd
Current assignee: Lucky Huaguang Graphics Co Ltd
Priority date: 2017-07-17
Filing date: 2017-07-17
Publication date: 2022-03-11
Anticipated expiration: 2037-07-17
Also published as: CN109265649A

Abstract

The invention discloses a self-emulsifying radiation curing composition, which is formed by dispersing an addition product generated by the reaction of monohydroxy unsaturated acrylate, hydroxyl-terminated polyethoxy (methyl) acrylate and diisocyanate under the catalysis of a catalyst in water at a high speed. It is a water-based radiation curing material, does not contain solvent, is environment-friendly in the using process and does not pollute the environment; the composition contains acrylic acid activated double bonds, and has the advantages of low price and high photocuring activity; the composition contains an amino ester bond, and has the advantages of good flexibility and high tensile strength; the polyether self-emulsifying technology is adopted, and no emulsifier is added, so that the material is more environment-friendly than other external-emulsifying water-based radiation curing materials; the high-efficiency urethanization reaction replaces the traditional esterification equilibrium reaction, the reaction does not generate water as a byproduct, the water as the byproduct is not required to be removed, and the production and preparation process is simple, energy-saving and environment-friendly.

Description

Self-emulsifying radiation curing composition and preparation method thereof

Technical Field

The invention belongs to the field of chemical technology green materials, and particularly relates to a self-emulsifying radiation curing composition and a preparation method thereof.

Background

Polyfunctional unsaturated acrylate monomers are widely used in the radiation curing art, and commonly used monomers are 1, 6-hexanediol diacrylate, pentaerythritol monoacrylate, diacrylates, triacrylates and tetraacrylates, hydroxypropyl glyceryl triacrylate, hydroxyethyl trimethylolpropane triacrylate, polyethylene glycol dimethacrylate, and the like. Nanjing university CN1021992792 discloses a method for preparing urethane acrylate by reacting soybean oil polyol with isophorone diisocyanate to generate a prepolymer and then reacting the prepolymer with hydroxyethyl acrylate; advanced materials research institute of Beijing university of chemical industry discloses a method for producing acetal pentaerythritol acrylate by reacting pentaerythritol with a small amount of aldehyde ketone and then esterifying the reaction product with acrylic acid; the advanced materials research institute CN104448212A of Beijing university of chemical industry also discloses an epoxy resin modified polyurethane acrylate; japanese first industrial pharmaceutical corporation WO2014061539 discloses a urethane acrylate and a reaction composition thereof, which improve curing properties such as shrinkage.

In order to protect the ecological environment and realize sustainable development, the current state advocates green manufacturing vigorously. In the field of chemical industry, green chemistry is advocated, raw materials are effectively utilized when chemical products are manufactured and applied, wastes are eliminated, toxic and dangerous reagents and solvents are avoided, and zero emission or zero pollution is realized. The development focus of green chemistry not only realizes green manufacturing in the production and development process, but also develops green chemicals with high technical content by adopting advanced scientific and technical means.

One of the hot spots in the development of radiation curing materials at present is the development of zero-emission, green and environment-friendly products.

The radiation curing technology is a processing technology for polymerizing liquid radiation curing materials into a solid state at a high speed through certain radiation waves including visible light, non-visible light, heat, electron beams and the like, and is widely applied to various fields of imaging materials, microelectronic manufacturing, functional film material production and the like. In order to reduce the viscosity of the radiation-curable material during processing, a diluent is added to reduce its viscosity and facilitate further processing. The diluents are divided into hydrocarbon solvents, particularly aliphatic hydrocarbons such as No. 200 solvent gasoline, kerosene and aromatic hydrocarbons such as benzene, toluene, xylene, No. 200 coal tar solvent and the like; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, etc., ketone solvents such as acetone, butanone, cyclopentanone, methyl isobutyl ketone, etc.; alcohol solvents such as methanol, ethanol, butanol, etc.; ether solvents such as ethylene glycol-ethyl ether, ethylene glycol-butyl ether, diethylene glycol-ethyl ether, etc.). Such as banana oil: for industrial use, the components are 5% of butanol, 21% of toluene, 5% of xylene, 15% of butyl acetate and 12% of ethyl acetate, the Tianna water mainly comprises ethyl acetate, n-butyl acetate, n-butanol, acetone, benzene, xylene and the like, and the diluents are all organic solvents in fact, so that the diluents directly or indirectly cause harm to people and pollute the environment.

Disclosure of Invention

In order to solve the above problems, the present invention provides a self-emulsifying radiation-curable composition and a method for preparing the same.

The object of the invention is achieved in the following way:

a self-emulsifying radiation-curable composition is formed by dispersing in water at high speed an addition product formed by the reaction of monohydroxy unsaturated acrylate, hydroxyl-terminated polyethoxy (meth) acrylate and diisocyanate under the catalysis of a catalyst.

The monohydroxy unsaturated acrylate is at least one of pentaerythritol triacrylate and hydroxyethyl (meth) acrylate.

The molecular weight of the hydroxyl-terminated polyethoxy (meth) acrylate is 500-5000.

The diisocyanate is at least one of toluene diisocyanate, 1, 6-hexamethylene diisocyanate and 4,4' -diisocyanate dicyclohexylmethane.

The ratio of the total moles of the monohydroxy unsaturated acrylate and the hydroxyl-terminated polyethoxy (meth) acrylate to the moles of diisocyanate is 2: 1.

The hydroxyl-terminated polyethoxy (meth) acrylate accounts for 20-50% of the total charge of all hydroxyl-containing acrylates.

The catalyst is an amine compound or an organic metal compound.

The amine compound is triethylene diamine, and the organic metal compound is dibutyltin dilaurate.

The mole number of the catalyst is 0.01-0.1% of that of diisocyanate.

The solid content in the composition is 10-80%.

The solids content of the composition is 20% to 70%.

Adding a phenol or quinone polymerization inhibitor into the addition product.

The addition amount of the phenol or quinone polymerization inhibitor accounts for 0.01-0.1% of the total weight of the addition product.

The phenol polymerization inhibitor is polyhydric phenol or substituted phenol.

The quinone polymerization inhibitor is benzoquinone or naphthoquinone.

The preparation method of the self-emulsifying radiation curing composition comprises the following specific steps: and (2) mixing the monohydroxy unsaturated acrylate, the hydroxyl-terminated polyethoxy (methyl) acrylate, the diisocyanate and the catalyst, stirring uniformly, reacting at 50-90 ℃ to obtain an addition product, dropwise adding and dispersing the addition product into water under the action of high-speed shearing, wherein the high-speed shearing revolution is more than 12000 r/min, and thus obtaining the stable self-emulsifying radiation curing composition.

Adding phenol or quinone polymerization inhibitor into the addition product.

Compared with the prior art, the self-emulsifying radiation curing composition disclosed by the invention is a green environment-friendly radiation curing monomer material, and also discloses a production preparation method thereof.

The self-emulsifying radiation curing composition and the preparation method thereof disclosed by the invention have the following characteristics:

1. it is a water-based radiation curing material, does not contain solvent, is environment-friendly in the using process and does not pollute the environment;

2. the composition contains acrylic acid activated double bonds, and has the advantages of low price and high photocuring activity;

3. the composition contains an amino ester bond, and has the advantages of good flexibility and high tensile strength;

4. the polyether self-emulsifying technology is adopted, and no emulsifier is added, so that the material is more environment-friendly than other external-emulsifying water-based radiation curing materials;

5. the high-efficiency urethanization reaction replaces the traditional esterification equilibrium reaction, the reaction does not generate water as a byproduct, the water as the byproduct is not required to be removed, and the production and preparation process is simple, energy-saving and environment-friendly.

The self-emulsifying radiation-curable composition of the present invention can be applied to all radiation-curing fields.

Detailed Description

The following are examples of the present invention, but the present invention is not limited to the following examples.

The main raw materials are abbreviated and obtained as follows: pentaerythritol triacrylate PETA: tianjin Tianjiao chemical; hydroxyethyl methacrylate HEMA, hydroxyethyl acrylate HEA are both from Mitsubishi Yang Japan; hydroxyl-terminated polyethylene glycol methacrylate PEGMA-OH, PEGA-OH, all from Sigma-Adrich, UK; hexamethylene diisocyanate HDI, cyclohexylmethane diisocyanate H12MDI, toluene diisocyanate TDI were all from Bayer Germany, dibutyltin dilaurate DY-12, triethylenediamine TEDA were all from Tianjin chemical reagent II.

Diisocyanates include aromatic diisocyanate Toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate (PPDI), Naphthalene Diisocyanate (NDI), dimethylbiphenyl diisocyanate (TODI); aliphatic and cycloaliphatic isomers are 1, 6-Hexamethylene Diisocyanate (HDI), 1-isocyanate-3-isocyanatomethylene-3, 5, 5-trimethyl-cyclohexyl (isophorone diisocyanate, IPDI), 4' -diisocyanate dicyclohexylmethane (H12MDI), Xylylene Diisocyanate (XDI), cyclohexane diisocyanate (CHDI), tetramethylxylylene diisocyanate (TMXDI), 1, 3-bis (isocyanatomethyl) cyclohexane (H6XDI), and the like. The diisocyanate raw material used in the present invention is preferably at least one of toluene diisocyanate, 1, 6-hexamethylene diisocyanate and 4,4' -diisocyanate dicyclohexylmethane.

The ratio of the total moles of monohydroxy unsaturated acrylate and hydroxyl terminated polyethoxy (meth) acrylate to the moles of diisocyanate is 2: 1.

The percentage of hydroxyl-terminated polyethoxy (meth) acrylate in the total charge of all hydroxyl-containing acrylates is 20 to 50%.

The catalyst is amine compound or organic metal compound.

The amine compound is triethylenediamine and the organometallic compound is dibutyltin dilaurate.

The mole number of the catalyst is 0.01-0.1% of that of the diisocyanate.

The solid content of the composition is 10-80%.

The solid content of the composition is 20-70%.

Phenol or quinone polymerization inhibitor is added into the addition product, which is favorable for normal temperature storage, transportation, sale and other links.

The phenolic polymerization inhibitor is polyhydric phenol or substituted phenol, such as hydroquinone, catechol, p-methoxyphenol, etc.

The quinone polymerization inhibitor is benzoquinone or naphthoquinone, such as p-benzoquinone, tetrachlorobenzoquinone, l, 4-naphthoquinone, etc.

The reaction can be bulk reaction or solution reaction, and the bulk reaction is preferably adopted, so that the transfer effect of a reaction solvent is less, and the reaction is more sufficient; in theory, solution reaction can also be adopted, the reaction heat effect is small, and the reaction speed is easier to control, but the solution solvent adopted in the reaction needs to contain no water or active hydrogen solvent, so that the damage of water or active hydrogen isocyanate groups in the solvent is avoided. The solution reaction product contains a solvent, which is not environment-friendly, so the reaction of the invention is preferably bulk reaction, the urethane reaction can be carried out in the range of normal temperature to 160 ℃, and the invention is preferably 50-90 ℃ in order to ensure that the production efficiency and the active double bond are not damaged by high temperature.

The urethane reaction catalyst is widely used, and there are acid catalysts, base catalysts, amine compounds, organometallic compounds, and the like. The reaction catalyst is selected from amine compounds and organic metal compounds, wherein the amine compounds comprise triethylene diamine (TEDA), Dimethylcyclohexylamine (DMCHA), Dimethylethanolamine (DMEA), Tetramethylbutanediamine (TMBDA), dimethylamino bis-ethyl ether (A-99) Benzyl Dimethylamine (BDMA) and the like; organometallic compounds such as organometallic compounds of mercury, lead, tin, bismuth, zinc, iron, and the like, preferably amine compounds such as triethylenediamine, organometallic compounds such as dibutyltin dilaurate, and the catalysts are preferably used in a molar amount of 0.001 to 1% by mole of diisocyanate; preferred amine compounds such as triethylenediamine and organic metal compounds such as dibutyltin dilaurate are used as the reaction catalyst of the present invention, and the amount of the catalyst used is preferably 0.01 to 0.1 mol% based on the diisocyanate.

Adding phenol or quinone polymerization inhibitor into the addition product.

Example 1

298g of PETA, 104.11g of HEMA, 100g of PEGMA-OH (molecular weight 500) and 0.063gDY-12 are added into a 1000 ml four-neck flask with a temperature-controlled heating device, a mechanical stirring device, a condensation device and a nitrogen protection device and stirred uniformly, 168.2g of HDI is dropwise added at 50 ℃ for 10 minutes, the mixture is reacted for 2 hours and then cooled to room temperature, and 0.067g of hydroquinone is added. The reaction product was added dropwise to 287g of water under high shear at 12000r/m, and the high shear was terminated after 3 hours.

Example 2

298g of PETA, 107.63g of HEMA, 173.25g of PEGMA-OH (molecular weight 1000) and 0.63gDY-12 are added into a 1000 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation device and a nitrogen protection device, evenly stirred, 168.2g of HDI is dropwise added at 60 ℃, dropwise added for 10 minutes, reacted for 2 hours, cooled to room temperature, and then 0.75g of catechol is added. The reaction product was added dropwise to 498g of water under 14000r/m high shear and the high shear was completed after 3 hours.

Example 3

298g of PETA, 92.90g of HEA, 391.30g of PEGMA-OH (molecular weight 2000) and 0.11g of TEDA are added into a 2000 ml four-neck flask with a temperature-controlled heating device, a mechanical stirring device, a condensation device and a drying tube and a nitrogen protection device, evenly stirred, 262.3g of H12DI is dropwise added at 70 ℃ for 10 minutes, the reaction is carried out for 2 hours, then the temperature is reduced to room temperature, and 0.68g of p-methoxyphenol is added. The reaction product was added dropwise to 1044.5g of water under high shear at 16000r/m and the high shear was completed after 3 hours.

Example 4

298g of PETA, 105.60g of HEA, 910.31g of PEGA-OH (molecular weight 4000) are added into a 2000 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation device, a drying tube and a nitrogen protection device, 0.51gDY-12 is evenly stirred, 262.3g of H12DI is dropwise added at 80 ℃ for 10 minutes, the reaction is carried out for 2 hours, then the temperature is reduced to room temperature, and 0.48g of p-benzoquinone is added. The reaction product was added dropwise to 2364g of water under 18000r/m high-speed shearing, and the reaction was terminated after 3 hours of high-speed shearing.

Example 5

298g of PETA, 127.4g of HEMA, 106.8g of PEGMA-OH (molecular weight 5000) and 0.51gDY-12 are added into a 1000 ml four-neck flask with a temperature-controlled heating, mechanical stirring, condensation and drying tube and a nitrogen protection device and are stirred uniformly, 174.16g of TDI is dropwise added at 70 ℃ for 10 minutes, the reaction is carried out for 2 hours, then the temperature is reduced to room temperature, and 0.85g of tetrachlorobenzoquinone is added. The reaction product was added dropwise to 1647.3g of water under high shear at 22000r/m, and the high shear was terminated after 3 hours.

Example 6

298g of PETA, 105.6g of HEA, 268.1g of PEGMA-OH (molecular weight 3000) and 0.51gDY-12 are added into a 1000 ml four-neck flask with a temperature control heating, mechanical stirring, condensation and drying tube and a nitrogen protection device and are stirred uniformly, 174.16g of TDI is dropwise added at 70 ℃ for 10 minutes, the reaction is carried out for 2 hours, then the temperature is reduced to room temperature, and 0.75g of hydroquinone is added. The reaction product was added dropwise to 3382g of water under 20000r/m high shear and the high shear was completed after 3 hours.

Example 7

298g of PETA, 112.1g of HEA, 101.5g of PEGMA-OH (molecular weight 3000) and 0.51gDY-12 are added into a 1000 ml four-neck flask with a temperature control heating, mechanical stirring, condensation and drying tube and a nitrogen protection device and stirred uniformly, 168.2g of HDI is dropwise added at 70 ℃ for 10 minutes, the mixture is reacted for 2 hours and then cooled to room temperature, and 0.90g l, 4-naphthoquinone is added. The reaction product was added dropwise to 1586g of water under high shear at 17000r/m for 3 hours.

Example 8

574g of PETA, 143.7g of PEGMA-OH (molecular weight 2000) and 0.11g of TEDA are added into a 2000 ml four-neck flask with a temperature-controlled heating device, a mechanical stirring device, a condensing device and a drying tube and a nitrogen protection device, stirred uniformly, 262.3g of H12DI is added dropwise at 70 ℃ for 10 minutes, the reaction is carried out for 2 hours, then the temperature is reduced to room temperature, and 0.80g of tetrachlorobenzoquinone is added. The reaction product was added dropwise to 2287g of water under high shear of 16000r/m, and the high shear was terminated after 3 hours.

Example 9

126.0g of HEA, 64.0g of PEGMA-OH (molecular weight 2000), 0.51g of 0.51gDY-12 are added into a 500 ml four-neck flask with a temperature-controlled heating device, a mechanical stirring device, a condensing device and a drying tube and a nitrogen protection device, stirred uniformly, 168.2g of HDI is dropwise added at 70 ℃ for 10 minutes, the mixture is reacted for 2 hours, then the temperature is reduced to room temperature, and 0.25g of hydroquinone is added. The reaction product was added dropwise to 89.5g of water under 19000r/m high shear and the high shear was terminated after 3 hours.

Example 10

298g of PETA, 92.90g of HEA, 391.30g of PEGMA-OH (molecular weight 2000) and 0.11g of TEDA are added into a 2000 ml four-neck flask with a temperature-controlled heating device, a mechanical stirring device, a condensation device and a drying tube and a nitrogen protection device, evenly stirred, 262.3g of H12DI is dropwise added at 70 ℃ for 10 minutes, the reaction is carried out for 2 hours, then the temperature is reduced to room temperature, and 0.68g of hydroquinone is added. The reaction product was added dropwise to 9404g of water under high-speed shearing at 16000r/m, and the reaction was terminated after 3 hours of high-speed shearing.

Example 11

298g of PETA, 104.11g of HEMA, 100g of PEGMA-OH (molecular weight 500) and 0.063gDY-12 are added into a 1000 ml four-neck flask with a temperature-controlled heating device, a mechanical stirring device, a condensation device and a nitrogen protection device and stirred uniformly, 168.2g of HDI is dropwise added at 50 ℃ for 10 minutes, the mixture is reacted for 2 hours and then cooled to room temperature, and 0.067g of hydroquinone is added. The reaction product was added dropwise to 95.7g of water under high shear at 12000r/m, and the high shear was terminated after 3 hours.

Example 12

220.6g of HEA, 201.2g of PEGMA-OH (molecular weight 2000), 0.51g of 0.51gDY-12 g of HDI are added into a 500 ml four-neck flask with a temperature-controlled heating device, a mechanical stirring device, a condensing device and a nitrogen protection device and stirred uniformly, 168.2g of HDI is added dropwise at 70 ℃ for 10 minutes, the mixture is reacted for 2 hours and then cooled to room temperature, and 0.25g of hydroquinone is added. The reaction product was added dropwise to 590.5g of water under 19000r/m high shear, and the reaction was terminated after 3 hours of high shear.

Example 13

247.3g of HEMA, 201.2g of PEGMA-OH (molecular weight 2000), 0.51g of 0.51gDY-12 g of HDI, 10 minutes of HDI and 0.25g of p-benzoquinone are added into a 500 ml four-neck flask with a temperature-controlled heating, mechanical stirring, condensation and drying tube and a nitrogen protection device and stirred uniformly, 168.2g of HDI is added dropwise at 70 ℃, the reaction is carried out for 2 hours, then the temperature is reduced to room temperature, and the p-benzoquinone is added. The reaction product was added dropwise to 590.5g of water under 19000r/m high shear, and the reaction was terminated after 3 hours of high shear.

Example 14

298g of PETA, 127.4g of HEMA, 106.8g of PEGMA-OH (molecular weight 5000), 0.51gDY-12 g of PEGA, 84.1g of TDI and 70 ℃ are added dropwise into a 1000 ml four-neck flask with a temperature-controlled heating device, a mechanical stirring device, a condensation device, a drying tube and a nitrogen protection device, the mixture is uniformly stirred, 87.1g of TDI and 84.1g of HDI are added dropwise at 70 ℃ for 10 minutes, the reaction is carried out for 2 hours, then the temperature is reduced to room temperature, and 0.52g of hydroquinone is added. The reaction product was added dropwise to 1647.3g of water under high shear at 22000r/m, and the high shear was terminated after 3 hours.

Example 15

298g of PETA, 127.4g of HEMA, 106.8g of PEGMA-OH (molecular weight 5000), 0.51gDY-12 g of PEGA-OH are added into a 1000 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation device and a drying tube and a nitrogen protection device, the mixture is stirred uniformly, 131.2g of H12MDI and 84.1g of HDI are dropwise added at 70 ℃ for 10 minutes, the mixture is reacted for 2 hours and then cooled to room temperature, and 0.52g of hydroquinone is added. The reaction product was added dropwise to 1647.3g of water under high shear at 22000r/m, and the high shear was terminated after 3 hours.

Example 16

298g of PETA, 127.4g of HEMA, 106.8g of PEGMA-OH (molecular weight 5000), 0.51gDY-12 g of PETA, 87.1g of TDI and 131.2g of H12MDI are added dropwise at 70 ℃ and stirred uniformly in a 1000 ml four-neck flask with a temperature-controlled heating device, a mechanical stirring device, a condensation device and a drying tube and a nitrogen protection device, the reaction is carried out for 2 hours, then the temperature is reduced to room temperature, and 0.52g of hydroquinone is added. The reaction product was added dropwise to 1647.3g of water under high shear at 22000r/m, and the high shear was terminated after 3 hours.

Example 17

298g of PETA, 127.4g of HEMA, 106.8g of PEGMA-OH (molecular weight 5000), 0.51gDY-12 g of PEGA-OH are added into a 1000 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation device and a drying tube and a nitrogen protection device, the mixture is uniformly stirred, 104.9g of H12MDI, 50.5g of HDI and 52.3g of TDI are dropwise added at 70 ℃, the mixture is dropwise added for 10 minutes, the reaction is carried out for 2 hours, the temperature is reduced to room temperature, and 0.52g of hydroquinone is added. The reaction product was added dropwise to 1647.3g of water under high shear at 22000r/m, and the high shear was terminated after 3 hours.

The application field is as follows: the composition is a green and environment-friendly water-based radiation curing product, contains active double bonds and urethane bonds, has the advantages of environmental protection, high photocuring activity, good flexibility and wear resistance, and can be widely applied to the radiation curing field such as the printing industry, coating, printing ink, protective film materials, automobile manufacturing industry, building material industry, printed circuit boards, large-scale integrated circuits, digital cameras, compact discs, mobile phones, liquid crystal displays, ion displays and other manufacturing fields. The following are examples of applications of the product of the present invention, but the present invention is not limited to the following examples.

Application example 1: in the printing field, a treatment-free infrared laser imaging printing plate is manufactured (each component is in parts by weight).

Phenolic resin 20

Synthesis of product 70 of example 1

Diaryl iodonium hexafluorophosphate 2.5

Infrared radiation absorbing dye ADS 8301

Nitroxyl radical piperidinol 0.5

0.5 parts of basic brilliant blue

Surfactant (BYK 306) 0.5

Methyl ethyl ketone 200

1-methoxy-2-propanol 700

The plate thus obtained was subjected to Kodak-win thermosensitive CTP plate-making machine at 120mJ/cm²The energy is used for exposure, and the printing is directly carried out on a machine, the blank density is 0.03, the screen dots are reduced by 1 to 99 percent, the printing endurance is 18.5 ten thousand printing times, and the imaging and printing performances are excellent.

Application example 2: in the field of optical hardening films: coating the following coating liquid on a terylene optical film base, controlling the coating weight, controlling the dry film thickness to be about 3um, and carrying out UV exposure and curing conditions: the leveling time is 25 ℃ for 2 min; the illumination intensity is 1000-². The hardness of the pencil of the test product reaches 3H, and the 0# steel wool does not leak the bottom after being rubbed for 50 times, and has excellent scratch resistance.

Water-based initiator Q-BTC-1 (International Bio-Synthesis Co.) 0.5g

Synthesis of example 9 product 100g

Application example 3: in the field of microelectronics, dry films of resists are produced. Printing with the following coating liquids

Water-based initiator Q-BTC-7 (International Bio-Synthesis) 1g

Synthesis of example 4 product 100g

The manufactured double-sided hole metallized printed circuit board has the advantages that the size of bubbles and pinholes is less than 0.05mm, the number of the bubbles and the pinholes per square meter is less than 10, the image edge is clear, and no broken line or flaw exists.

Application example 4: the water-based flocking adhesive is prepared in the field of manufacturing environment-friendly bonding functional materials, such as textile industry. Basic formula of the adhesive:

water-based initiator Q-BTC-4 (International Bio-Synthesis) 1g

Synthesis of example 8 product 100g

The obtained flocking adhesive has the acrylic fiber peeling strength of 60N/cm and the shearing strength of 30 MPa.

Application example 5: in the environment-friendly coating industry, the light-cured emulsion paint is prepared. The basic formula of the emulsion paint is as follows:

water-based initiator Q-BTC-2 (International Bio-Synthesis Co.) 2.5g

Synthesis of example 10 product 1000g

Preparing a standard test strip of a latex paint film, and performing ultraviolet exposure test, wherein the pencil hardness is 3H, the elasticity of the paint film is 92%, and the adhesive force of film glass is as follows: 25 newtons per inch, elongation to crack > 40%.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the overall concept of the present invention, and these should also be considered as the protection scope of the present invention.

Claims

1. A self-emulsifying radiation-curable composition characterized by: the composition is formed by dispersing an addition product generated by the reaction of monohydroxy unsaturated acrylate, hydroxyl-terminated polyethoxy (methyl) acrylate and diisocyanate under the catalysis of a catalyst in water at a high speed; the monohydroxy unsaturated acrylate is at least one of pentaerythritol triacrylate and hydroxyethyl (meth) acrylate; the molecular weight of the hydroxyl-terminated polyethoxy (meth) acrylate is 500-5000.

2. The self-emulsifying radiation-curable composition of claim 1, wherein: the diisocyanate is at least one of toluene diisocyanate, 1, 6-hexamethylene diisocyanate and 4,4' -diisocyanate dicyclohexylmethane.

3. The self-emulsifying radiation-curable composition of claim 1, wherein: the ratio of the total moles of the monohydroxy unsaturated acrylate and the hydroxyl-terminated polyethoxy (meth) acrylate to the moles of diisocyanate is 2: 1.

4. The self-emulsifying radiation-curable composition of claim 1, wherein: the hydroxyl-terminated polyethoxy (meth) acrylate accounts for 20-50% of the total charge of all hydroxyl-containing acrylates.

5. The self-emulsifying radiation-curable composition of claim 1, wherein: the catalyst is an amine compound or an organic metal compound.

6. The self-emulsifying radiation-curable composition of claim 5, wherein: the amine compound is triethylene diamine, and the organic metal compound is dibutyltin dilaurate.

7. The self-emulsifying radiation-curable composition of claim 1, wherein: the mole number of the catalyst is 0.01-0.1% of that of diisocyanate.

8. The self-emulsifying radiation-curable composition of claim 1, wherein: the solid content in the composition is 10-80%.

9. The self-emulsifying radiation-curable composition of claim 8, wherein: the solids content of the composition is 20% to 70%.

10. The self-emulsifying radiation-curable composition of claim 1, wherein: adding a phenol or quinone polymerization inhibitor into the addition product.

11. The self-emulsifying radiation-curable composition of claim 10, wherein: the addition amount of the phenol or quinone polymerization inhibitor accounts for 0.01-0.1% of the total weight of the addition product.

12. The self-emulsifying radiation-curable composition of claim 10, wherein: the phenol polymerization inhibitor is polyhydric phenol or substituted phenol.

13. The self-emulsifying radiation-curable composition of claim 10, wherein: the quinone polymerization inhibitor is benzoquinone or naphthoquinone.

14. A process for preparing a self-emulsifying radiation-curable composition according to any one of claims 1 to 13, characterized in that: the method comprises the following specific steps: and (2) mixing the monohydroxy unsaturated acrylate, the hydroxyl-terminated polyethoxy (methyl) acrylate, the diisocyanate and the catalyst, stirring uniformly, reacting at 50-90 ℃ to obtain an addition product, dropwise adding and dispersing the addition product into water under the action of high-speed shearing, wherein the high-speed shearing revolution is more than 12000 r/min, and thus obtaining the stable self-emulsifying radiation curing composition.

15. The method of preparing a self-emulsifying radiation-curable composition according to claim 14, wherein: adding phenol or quinone polymerization inhibitor into the addition product.