CN102220062B - Aqueous UV curing coating and preparation method thereof - Google Patents

Abstract

The invention relates to an aqueous nanometer UV curing coating and a preparation method thereof, belonging to the technical field of environmentally friendly coatings. The coating provided in the invention comprises surface modified silica sol grafted epoxy acrylate prepolymers, functional monomers, a photoinitiator and a coating additive. According to the invention, polar groups are introduced into the prepolymers through the functional monomers and the groups and the prepolymers are neutralized into a salt so as to enable the coating to uniformly disperse in water, being in accordance withenvironmental protection requirements; the addition of nanometer silica sol in the coating enables the coating to have high transparency and hardness and good wear resistance; the manner of spraying,blade coating or spin coating is employed and a film with characteristics of good weatherability, adhesion and anti-corrosion is formed by UV curing, thereby realizing automatic streamline coating and convenient construction. The coating is used for the surfaces of timber, metal, plastic, printing ink, cigarette package materials, printing paper, fibers and automobiles.

Description

A kind of water-based UV is coating material solidified and preparation method thereof

Technical field

It is coating material solidified and preparation method thereof to the present invention relates to a kind of water-based UV, belongs to the environmental protection coating material technical field.

Background technology

From German Bayer AG in 1967 develop first-generation UV coating material solidified since, but the UV curing technology has worldwide obtained develop rapidly with numerous advantages such as operation under the fast room temperature of its curing speed, less energy-consumption, coating performance excellence.UV is coating material solidified, printing ink, solder resist and tackiness agent etc. are applied rapidly in electronics, printing, building, decoration, medicine, machinery, chemical industry and automobile and other industries, has become new technology branch and a developing direction.In addition, UV is coating material solidified because its good performance meets the demand that current people's environmental consciousness constantly strengthens, and has huge development potentiality.Abroad, the coating material solidified different field such as building coating, sports goods, telecommunications, wrapping material and automobile that have been widely used in of UV.China's photocuring field tempo is more surprising, and is annual all with 20%～30% speed increment.Use more and more widely in every field, as having obtained good application at base materials such as paper, woodenware, plastics, metal, CD, optical fiber.Current, the coating material solidified development of UV is faced with perfect opportunity again, implements the strategy of sustainable development for cooperating, and China has formulated environmental protection policy, and has strengthened law enforcement dynamics, and people's environmental consciousness strengthens day by day, and increasing people can select environmentfriendly products.

Traditional UV curing system mainly is made up of light trigger, oligopolymer, reactive thinner (monomer) and auxiliary agent, as CN1310161, CN1380366 and CN1371926 etc., report adopts the reactive thinner replace organic solvent to reduce system viscosity and plays crosslinked action, effectively reduces the VOC quantity discharged; But these reactive thinner major parts have low-steam pressure, toxicity and pungency, still can remain in the product after illumination finishes, and environment and HUMAN HEALTH are produced detrimentally affect, and the degree of monomer reduction system viscosity is also limited.The general viscosity of the oligopolymer that relative molecular mass is bigger is bigger, and is difficult to regulate control, so non-aqueous UV curing system is difficult to accomplish to prepare without thinner the photocuring system of 100% solid content.

For fear of using reactive thinner to reduce the VOC discharging, improve the over-all properties of UV curing system, environmentally friendly water-based UV curing system day by day becomes the new research direction of printing material industry and development trend.The UV solidified aqueous coating combines the advantage of water-borne coatings and photo-cured coating, is developed rapidly in recent years, also is one of main developing direction of photo-cured coating from now on.The advantage of UV solidified aqueous coating is: can use the very high oligomer of relative molecular mass to improve the bonding strength to some base material, and other physicalies of raising cured film, and be subjected to the restriction of working viscosity unlike the oligomer relative molecular mass of traditional UV coating: the viscosity used water of system is regulated, and needn't use diluting monomer, so just can avoid the contraction that is caused by activity diluting monomer; Can obtain coating as thin as a wafer in this way, and equipment is easy to clean; Water oven dry back just can obtain touching the coating of doing before irradiation, can be used for the surface cure of three-dimensional body like this, just touched the coating of doing before this irradiation, had reduced the absorption of dust, and can the defective to coating repair before curing.As CN101210391, CN101914171A, CN101613449, CN101967323A, CN101845259A and CN101629050 etc., disclose the employing emulsifying agent or introduced a large amount of polar groups, thereby obtained water-based UV curing system.Water replaces the reactive thinner in traditional UV curing system, has solved because the problems such as environmental pollution, pungency and insecurity that volatile organic constituent causes are a kind of technology and technology that combines water-based system and UV curing technology advantage.But the shortcoming of waterborne UV coating is: must dewatered drying before the photocuring, and the system glossiness is low, poor solvent resistance, scuff resistance is poor, and film forming properties, and over-all properties especially is as weathering resistance, increase hard wear resistance, temperature tolerance and erosion resistance equal difference.

Summary of the invention

Technical problem to be solved by this invention is to provide the water-based UV of high comprehensive performance of the good and paint film of glossiness in a kind of UV solidification process coating material solidified.

The present invention's original position in epoxy acrylic ester prepolymer is introduced Nano silica sol, because Nano silica sol contains a large amount of silicon hydroxyls, in prepolymer Water-borne modification process, increased the probability with the function monomer reaction, in the UV solidification process, defectives such as glossiness is low can be effectively overcome, the over-all properties of water-borne coatings film can also be effectively improved.

Technical scheme of the present invention is:

A kind of water-based UV is coating material solidified, and each component and quality percentage composition are as follows:

The preparation method that water-based UV provided by the present invention is coating material solidified may further comprise the steps:

(1) surface modification of Nano silica sol

Get Nano silica sol and silane coupling agent mixed grinding by proportioning, add deionized water again and mix, begin dropping ammonia after being warming up to 40 ℃, reaction 1-12h namely gets the Nano silica sol of surface modification, and each constituent mass percentage composition is as follows:

(2) preparation of silicon sol grafting epoxy acrylate water-based prepolymer

In the epoxy acrylic ester prepolymer for preparing, add the surface-modified nano silicon sol that step (1) makes by proportioning, under 300-500rpm stirs, be warming up to 50-65 ℃, reaction 3-6h, obtain silica sol modified epoxy acrylic ester prepolymer, then add Resorcinol, function monomer and triethylamine successively by proportioning in this prepolymer, described function monomer is a kind of in maleic anhydride, methylene-succinic acid and the FUMARIC ACID TECH GRADE; Reaction 2-8h, reaction process is added small amount of acetone and is increased the reaction system flowability, namely gets silicon sol grafting epoxy acrylate water-based prepolymer, and each constituent mass percentage composition is as follows:

(3) the coating material solidified preparation of water nano UV

Add Nano silica sol grafting epoxy acrylate water-based prepolymer, light trigger, defoamer, flow agent and sanitas by proportioning and stir, leaving standstill froth breaking, namely to get water-based UV coating material solidified.

Among the coating material solidified preparation method of above-mentioned water-based UV,

Described silane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, the propenyl Trimethoxy silane, the propenyl triethoxyl silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane or methacryloxypropyl three (isopropoxy) silane, the trifluoro propyl Trimethoxy silane, the trifluoro propyl dimethyl dichlorosilane (DMCS), trifluoro propyl methyl cyclotrisiloxane, ten trifluoro octyl group Trimethoxy silanes, the trifluoromethyl trimethyl silane, 1H, 1H, 2H, the mixture of one or more in 2H-perfluoro capryl front three (second) TMOS.

The preparation method of described epoxy acrylic ester prepolymer is: the preparation method of described epoxy acrylic ester prepolymer is: add Resins, epoxy in reaction vessel, be heated to 75 ℃ and stirring, drip the vinylformic acid of 2 times of amounts again, and an amount of Resorcinol and tetramethyl ammonium chloride prevent monomer polymerization, 1-2h dropwises, be warming up to 85-95 ℃ then, keep 4h, namely.

Described light trigger is any one or more than one the combination in 2-hydroxy-2-methyl-1-phenyl-acetone, 2-hydroxy-2-methyl-1-hydroxyl ether phenyl-acetone and the 1-hydroxy cyclohexyl phenylketone.

Light trigger is selected from the product of ciba company, the corresponding IRGACURE1173 of 2-hydroxy-2-methyl-1-phenyl-acetone; The corresponding IRGACURE2959 of the hydroxyl ether of 2-hydroxy-2-methyl-1-phenyl-acetone; The corresponding IRGACURE184. of 1-hydroxy cyclohexyl phenylketone

Described defoamer is the water-borne coatings defoamer, selects THIX278 or THIX318 for use.

Described flow agent is polymkeric substance, cellulose acetate or the ethyl cellulose of the poly-trisiloxanes of silicone oil, oxyethyl group modification, polyether-modified silicone resin, long alkyl chain silicone resin and acrylic resin.

Described sanitas is benzimidazolyl-2 radicals-Urethylane, zinc naphthenate, 2-(4-thiazolyl) benzoglyoxaline, dichlorophen, TMTD, tetrachloro isophthalonitrile, sodium pentachlorophenate, zinc oxide, orthoxenol, isothiazolinone, dimethyl fumarate, 2-bromo-2-nitro-1, ammediol, triphenyltin, rich d-limonene, third chrysanthemum ester or the artificial camphor.

The coating material solidified using method of water-based UV provided by the present invention is: coating adopts the mode of spraying, blade coating or spin coating to be applied to surfaces such as glass, metal, plastics or timber, Infrared Heating levelling, oven dry, recycling UV hardening with radiation film forming.

The present invention overcomes the shortcoming of existing waterborne UV coating, provides a kind of water nano UV coating material solidified.Be solvent with water, with Nano silica sol modification and UV film-forming, be a kind of good weatherability, hardness height, wear resistance is good, antiseptic property is excellent environmental protection coating material; Its macromolecule matrix resin adopts the Nano silica sol modification, with the function monomer reaction, in resin, introduce the Si-O-Si network then, simultaneously a large amount of polar group and unsaturated link(age)s introduced, it is dispersed and stable obviously to improve coating, and the processing characteristics of water-thinned nanometer paint.In addition, owing to introduce Nano silica sol in the system, when film-forming, can serve as linking agent, make the rapid film-forming of resin, nano particle is dispersed in the resin simultaneously, form smooth surface on its surface, thereby light is had higher reflectivity, make its surface have good glossiness.

Embodiment

The present invention further is illustrated by the following example, but non-in order to limit the scope of the invention.

Embodiment 1

Take by weighing 30g Nano silica sol (10nm), 0.6g gamma-methyl allyl acyloxypropyl trimethoxysilane and 10mL deionized water, ultrasonic 20min is warming up to 40 ℃, insulation 5h.Gained modified Nano silicon sol is joined in the 50g epoxy acrylic ester prepolymer for preparing, be warming up to 50-65 ℃, 3h under 300-500rpm stirs, obtain silica sol modified epoxy acrylic ester prepolymer, then add 0.5g Resorcinol, 5g maleic anhydride and 3g triethylamine successively, reaction 6h, reaction process is added 2mL acetone, namely gets silicon sol grafting epoxy acrylate water-based prepolymer.At last, in this reaction system, add 5gIRGACURE1173,0.5g THIX278, the modification of 0.5g oxyethyl group poly-trisiloxanes, 1g TMTD and 30g deionized water successively, stir namely.The coating that makes adopts the mode of spraying, blade coating or spin coating to be applied to surfaces such as glass, metal, plastics or timber, Infrared Heating levelling, oven dry, and recycling UV hardening with radiation film forming, its performance is as shown in table 1.

Table 1

Performance Test result Examination criteria Set time/s ??1 ??—— Stability in storage (50 ℃)/sky ??15 ??—— Sticking power/level ??0 ??GB/T?9286-1998 Hardness ??5H ??GB/T?6739-2006

Wear resistance/(750g, 500r) ??0.01 ??GB/T?1768-1989 Glossiness/degree ??98 ??GB/T?8807-1988

Embodiment 2

Take by weighing 40g Nano silica sol (mixture of 10nm, 5nm and 150nm), 0.75g gamma-methyl allyl acyloxypropyl trimethoxysilane and 10mL deionized water, ultrasonic 20min begins to drip the 0.2mL strong aqua after being warming up to 40 ℃, and 5h dropwises.Gained modified Nano silicon sol is joined in the 50g epoxy acrylic ester prepolymer for preparing, be warming up to 50-65 ℃, 3h under 300-500rpm stirs, obtain silica sol modified epoxy acrylic ester prepolymer, then add 0.5g Resorcinol, 5g maleic anhydride and 3g triethylamine successively, reaction 6h, reaction process 3.2mL acetone namely gets silicon sol grafting epoxy acrylate water-based prepolymer.At last, in this reaction system, add 5g IRGACURE1173,0.5g THIX278, the modification of 0.5g oxyethyl group poly-trisiloxanes, 1g TMTD and 30g deionized water successively, stir namely.The coating that makes adopts the mode of spraying, blade coating or spin coating to be applied to surfaces such as glass, metal, plastics or timber, Infrared Heating levelling, oven dry, and recycling UV hardening with radiation film forming, its performance is as shown in table 2.

Table 2

Performance Test result Examination criteria Set time/s ??0.6 ??—— Stability in storage (50 ℃)/sky ??18 ??—— Sticking power/level ??0 ??GB/T?9286-1998 Hardness ??6H ??GB/T?6739-2006 Wear resistance/(750g, 500r) ??0.02 ??GB/T?1768-1989 Glossiness/degree ??101 ??GB/T?8807-1988

Embodiment 3

Take by weighing 50g Nano silica sol (50nm), 0.8g gamma-methyl allyl acyloxypropyl trimethoxysilane and 20mL deionized water, ultrasonic 30min begins dropping ammonia after being warming up to 40 ℃, and 3h dropwises.Gained modified Nano silicon sol is joined in the 80g epoxy acrylic ester prepolymer for preparing, be warming up to 50-65 ℃, 3h under 300-500rpm stirs, obtain silica sol modified epoxy acrylic ester prepolymer, then add 1g Resorcinol, 5g maleic anhydride and 4.5g triethylamine successively, reaction 5h, reaction process is added 4.3mL acetone, namely gets silicon sol grafting epoxy acrylate water-based prepolymer.At last, in this reaction system, add 8g IRGACURE1173,0.5g THIX278, the poly-trisiloxanes of 0.5g oxyethyl group modification and 80mL deionized water successively, stir namely.The coating that makes adopts the mode of spraying, blade coating or spin coating to be applied to surfaces such as glass, metal, plastics or timber, Infrared Heating levelling, oven dry, and recycling UV hardening with radiation film forming, its performance is as shown in table 3.

Table 3

Performance Test result Examination criteria Set time/s ??1.1 ??—— Stability in storage (50 ℃)/sky ??13 ??—— Sticking power/level ??0 ??GB/T?9286-1998 Hardness ??6H ??GB/T?6739-2006 Wear resistance/(750g, 500r) ??0.01 ??GB/T?1768-1989 Glossiness/degree ??97 ??GB/T?8807-1988

Embodiment 4

Keep embodiment 3 other conditions constant, maleic anhydride is used methylene-succinic acid and FUMARIC ACID TECH GRADE successively.The coating that makes adopts the mode of spraying, blade coating or spin coating to be applied to surfaces such as glass, metal, plastics or timber, Infrared Heating levelling, oven dry, and recycling UV hardening with radiation film forming, the better performances of prepared film, its performance is as shown in table 4.

Table 4

Embodiment 5

Keep embodiment 3 other conditions constant, gamma-methyl allyl acyloxypropyl trimethoxysilane is used vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane, propenyl triethoxyl silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, trifluoro propyl Trimethoxy silane, trifluoro propyl dimethyl dichlorosilane (DMCS), trifluoro propyl methyl cyclotrisiloxane, ten trifluoro octyl group Trimethoxy silanes, trifluoromethyl trimethyl silane and 1H successively, 1H, 2H, 2H-perfluoro capryl front three (second) TMOS is replaced.The coating that makes adopts the mode of spraying, blade coating or spin coating to be applied to surfaces such as glass, metal, plastics or timber, Infrared Heating levelling, oven dry, recycling UV hardening with radiation film forming.

Embodiment 6

Keep embodiment 3 other conditions constant, IRGACURE1173 is replaced with IRGACURE2959 and IRGACURE184 successively.The coating that makes adopts the mode of spraying, blade coating or spin coating to be applied to surfaces such as glass, metal, plastics or timber, Infrared Heating levelling, oven dry, and recycling UV hardening with radiation film forming, the better performances of gained film, its performance is as shown in table 5.

Table 5

Claims (5)

1. the preparation method that water-based UV is coating material solidified is characterized in that, comprises the steps:

1) surface modification of Nano silica sol

Get Nano silica sol and silane coupling agent mixed grinding by proportioning, add deionized water again and mix, begin dropping ammonia after being warming up to 40 ℃, reaction l-12h namely gets the Nano silica sol of surface modification, and each constituent mass percentage composition is as follows:

Nano silica sol 0.1～80%

Silane coupling agent 0～8%

Ammoniacal liquor 0～1%

Water 15～95%

2) preparation of silicon sol grafting epoxy acrylate water-based prepolymer

In the epoxy acrylic ester prepolymer for preparing, add the surface-modified nano silicon sol that step (1) makes by proportioning, under 300-500rpm stirs, be warming up to 50-65 ℃, reaction 3-6h, obtain silica sol modified epoxy acrylic ester prepolymer, then add Resorcinol, function monomer and triethylamine successively by proportioning in this prepolymer, described function monomer is a kind of in maleic anhydride, methylene-succinic acid and the FUMARIC ACID TECH GRADE; Reaction 2-8h, reaction process is added small amount of acetone and is increased the reaction system flowability, namely gets silicon sol grafting epoxy acrylate water-based prepolymer, and each constituent mass percentage composition is as follows:

Surface-modified nano silicon sol 5～50%

Epoxy acrylic ester prepolymer 25～60%

Resorcinol 0.1～3%

Function monomer 0.5～5%

Triethylamine 0.1～10%

Acetone 0～30%

3) the coating material solidified preparation of water nano UV

Add Nano silica sol grafting epoxy acrylate water-based prepolymer 60～90% by proportioning, light trigger 3～10%, defoamer 0～1%, flow agent 0～1%, sanitas 0～3%, deionized water 5～35% stirs, and leaving standstill froth breaking, namely to get water-based UV coating material solidified,

The size of described Nano silica sol is in 5～200nm scope, and the content of all components of using in above-mentioned preparation process (1)-(3) all is not 0.

2. preparation method as claimed in claim 1, it is characterized in that: described silane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, the propenyl Trimethoxy silane, the propenyl triethoxyl silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane or methacryloxypropyl three (isopropoxy) silane, the trifluoro propyl Trimethoxy silane, the trifluoro propyl dimethyl dichlorosilane (DMCS), trifluoro propyl methyl cyclotrisiloxane, ten trifluoro octyl group Trimethoxy silanes, the trifluoromethyl trimethyl silane, 1H, 1H, 2H, the mixture of one or more in 2H-perfluoro capryl front three (second) TMOS.

3. preparation method as claimed in claim 1 or 2, it is characterized in that: the preparation method of described epoxy acrylic ester prepolymer is: add Resins, epoxy in reaction vessel, be heated to 75 ℃ and stirring, drip the vinylformic acid of 2 times of amounts again, and an amount of Resorcinol and tetramethyl ammonium chloride prevent monomer polymerization, and l-2h dropwises, and is warming up to 85-95 ℃ then, keep 4h, namely.

4. preparation method as claimed in claim 1 or 2, it is characterized in that: described light trigger is any one or more than one the combination in 2-hydroxy-2-methyl-1-phenyl-acetone, 2-hydroxy-2-methyl-1-hydroxyl ether phenyl-acetone and the 1-hydroxy cyclohexyl phenylketone.

5. preparation method as claimed in claim 1 or 2, it is characterized in that: described defoamer is the water-borne coatings defoamer, selects THIX278 or THIX318 for use.