A kind of epoxy ultraviolet-curing paint
Technical field
The present invention relates to a kind of coating, more particularly, to a kind of epoxy ultraviolet-curing paint.
Background technique
In the past few years, ultraviolet-curing paint fibre coating, CD coating/DVD adhesive, credit card, timber,
Very rapid development is suffered from beverage can, food packaging, journal surface, medical instrument and automobile industry.Ultraviolet light solidification
Coating possesses huge market potential, and the ratio in entire coating products increases year by year.Ultraviolet-curing paint master
It to be made of oligomer, monomer, photoinitiator and auxiliary agent.The cured key reaction course of ultraviolet light be caused by radiation it is light-initiated
Agent is decomposed, and is generated living radical and is caused monomer/oligomer polymerization crosslinking.
Resin used in ultraviolet light solidification at present is just substantially acrylic resin and two kinds of epoxy resin, middle ring
Oxygen resin is the organic compound referred in molecule containing two or more epoxy groups, in addition to individual, they opposite
Molecular mass is not high.The molecular structure of epoxy resin be in strand contain active epoxy group be its feature, epoxy
Group can be located at the end of strand, centre or circlewise structure.Due to containing active epoxy group in molecular structure, make
They can be crosslinked with a plurality of types of curing agent reacts and forms the insoluble high polymer with three-dimensional reticular structure.All point
High-molecular compound in minor structure containing epoxy group is referred to as epoxy resin.Epoxy resin after solidification has good object
Reason, chemical property, it has excellent adhesive strength to the surface of metal and nonmetallic materials, and dielectric properties are good, and deformation is received
Shrinkage is small, and product size stability is good, and hardness is high, and flexibility is preferable, to alkali and most of solvent-stable, thus is widely used in
National defence, each department of national economy are poured, impregnate, the purposes such as lamination material, bonding agent, coating.
However energy used in epoxies ultraviolet-curing paint photocuring on the market is higher at present, obtains after solidification
Although film hardness is higher, it is more crisp, can not impact resistance, high and low temperature resistance, and its not resistant not resistant to water.Such as one kind exists
A kind of UV photocuring sanding primer reported in Chinese patent literature, application publication number are 105315734 A of CN, the hair
It is bright to disclose a kind of UV photocuring sanding primer, which is characterized in that be made of the raw material of following weight percents: bisphenol A-type
Epoxy resin E-42 60-65%, benzophenone 2-3%, TPGDA 20-30%, n-butanol 10-15%, modified diamond dust 2-
3%, nanosized SiO_2 1-2%, defoaming agent 0.5-0.8%, dispersing agent 0.4-0.6%.UV photocuring sanding primer of the present invention is low
Volatilization, low smell, environmental pollution are small;With preferable hardness;It with good grinability, is easily sanded, while also having one
Fixed fillibility;Curing rate is fast, high production efficiency;Normal temperature cure is suitble to a variety of substrates;Energy saving, energy consumption is approximately tradition
The 1/5 of coating;The performance indicator of the organic solvents various aspects such as coating is wear-resisting, acid and alkali-resistance, salt spray resistance, resistance to gasoline is very high, especially
It is that its paint film is plentiful, gloss is especially prominent.But its there is also more deficiencies, although such as its have preferable hardness, its
Main resin is that its heat resistance of bisphenol A type epoxy resin and toughness is not high, is unable to satisfy daily use.
Summary of the invention
The present invention be in order to overcome photocureable coating not high-low temperature resistant in the prior art, the coating property obtained after solidification compared with
It is crisp, it is not resistant to water intolerant to greasy dirt the problem of, provide one kind can high-low temperature resistant, the coating property obtained after solidification is tough and tensile, water-fast resistance to
A kind of epoxy ultraviolet-curing paint of greasy dirt.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of epoxy ultraviolet-curing paint, it is composed of the following components according to parts by weight: bisphenol A type epoxy resin 60-
80 parts, 15-26 parts of bisphenol-A epoxy resin, 20-30 parts of borosilicate modified epoxy, glycerin triglycidyl ether 20-
35 parts, 5-15 parts of ethoxylated trimethylolpropane triacrylate, 5-8 parts of triaryl matte hexafluoro antimonate, azo two is different
1-2 parts of butyronitrile, 1-2 parts of benzoin isopropyl ether, 2-5 parts of fluorinated acrylate levelling agent.
Preferably, composed of the following components according to parts by weight: 65-75 parts of bisphenol A type epoxy resin, hydrogenated bisphenol A
18-25 parts of type epoxy resin, 20-30 parts of borosilicate modified epoxy, 25-30 parts of glycerin triglycidyl ether, ethoxylation
5-12 parts of trimethylolpropane trimethacrylate, 5-8 parts of triaryl matte hexafluoro antimonate, 1-2 parts of azodiisobutyronitrile are rested in peace
Fragrant isopropyl ether 1-2 parts, 2-5 parts of fluorinated acrylate levelling agent.
Preferably, composed of the following components according to parts by weight: 70 parts of bisphenol A type epoxy resin, hydrogenated bisphenol A type ring
22 parts of oxygen resin, 28 parts of borosilicate modified epoxy, 30 parts of glycerin triglycidyl ether, ethoxylated trimethylolpropane three
10 parts of acrylate, 6 parts of triaryl matte hexafluoro antimonate, 2 parts of azodiisobutyronitrile, 2 parts of benzoin isopropyl ether, fluorine-containing propene
4 parts of acid esters levelling agent.
Bisphenol A type epoxy resin and bisphenol-A epoxy resin have the advantages that hardness is high, intensity is high, but its toughness
It is poor, it is added to after borosilicate modified epoxy, can aid in promotion finally through the toughness of resin material.Further, since
For borosilicate modified epoxy due to containing Si-O-B structure in its main chain, high and low temperature resistance is superior, being capable of reinforced resin material
The high and low temperature resistance of material.Simultaneously because it is added to glycerin triglycidyl ether, three propylene of ethoxylated trimethylolpropane
The resin material of the low viscosities such as acid esters facilitates the viscosity for reducing whole system, and the addition of fluorinated acrylate levelling agent can
Guarantee the levelling of final resin, and due to its internal fluorine atom, makes the surface Waterproofing/oilproofing object after the completion of solidifying.In the present invention
It is acted synergistically using triaryl matte hexafluoro antimonate, azodiisobutyronitrile and benzoin isopropyl ether three different initiators,
It can effectively ensure that the completeness of photocuring and reduce the energy of photocuring.
The borosilicate modified epoxy the preparation method is as follows:
(a) there-necked flask takes 10 parts of boron under -20-0 DEG C and nitrogen atmosphere with constant pressure funnel according to parts by weight
Acid, 48-52 parts of triethylamines, 50 parts of organic solvents are added in there-necked flask and are sufficiently stirred, and are then added in constant pressure funnel
45-50 parts of dimethylchlorosilanes and 50 parts of organic solvents, are slowly added dropwise into there-necked flask, the reaction was continued 3-5 after being added dropwise
Hour, it is filtered to remove the triethylamine hydrochloride of generation after reaction, filtrate washes 3 times, organic solvent is removed under reduced pressure, obtains three
(dimethyl silicon substrate) borate.
(b) there-necked flask matches constant pressure funnel, under 80-100 DEG C and atmosphere, by three (diformazan obtained in step (a)
Base silicon substrate) 50 parts of borate, 50 parts, 0.05-0.2 parts platiniferous 2% of toluene platinum catalyst be added in there-necked flask, then in perseverance
It presses and 75-80 parts of allyl glycidyl ethers, 30 parts of toluene is added in dropping funel, be then slowly dropped in three-necked flask, drip
The reaction was continued after adding 4-6 hours, and 1-3 parts of active carbons are added after reaction and stir 0.5-2 hours, solvent is evaporated off in filtering
And low-boiling-point substance, obtain borosilicate modified epoxy.
Preferably, the organic solvent in the step (a) is tetrahydrofuran, anhydrous ether, methylene chloride, n-hexane
One of.
Preferably, the platinum catalyst of the step (b) is isopropyl alcohol solution of chloroplatinic acid, Karst catalyst, allyl
One of base silicon (oxygen) alkane platinum complex.
Preferably, the ultraviolet-curing paint the preparation method is as follows: each component is added according to parts by weight
Into container, then container is put into baking oven and increases temperature to 55-65 DEG C, heats 30-90 minutes, then takes out high-speed stirred
Dispersion 0.5-3 hours, then ultrasonic disperse 0.5-2 hours, obtains epoxy ultraviolet-curing paint.
Therefore, the invention has the following beneficial effects: energy needed for (1) photocuring is low;(2) resin system viscosity is lower;
(3) hardness of film height, high and low temperature resistance and good toughness after solidifying.
Technical solution of the present invention is made to further describe explanation below by specific embodiment.
If saying that the raw material of use is raw material commonly used in the art without specified otherwise, in the embodiment of the present invention, implement
Method employed in example, is the conventional method of this field.
Embodiment 1
A kind of epoxy ultraviolet-curing paint, it is composed of the following components according to parts by weight: bisphenol A type epoxy resin 60
Part, 15 parts of bisphenol-A epoxy resin, 20 parts of borosilicate modified epoxy, 20 parts of glycerin triglycidyl ether, ethyoxyl
Change 5 parts of trimethylolpropane trimethacrylate, 5 parts of triaryl matte hexafluoro antimonate, 1 part of azodiisobutyronitrile, benzoin isobutyl
1 part of propyl ether, 2 parts of fluorinated acrylate levelling agent.
The borosilicate modified epoxy the preparation method is as follows:
(a) there-necked flask match constant pressure funnel, under -20 DEG C and nitrogen atmosphere, take according to parts by weight 10 parts of boric acid,
48 parts of triethylamines, 50 parts of tetrahydrofurans are added in there-necked flask and are sufficiently stirred, and 45 part two is then added in constant pressure funnel
Methylchlorosilane and 50 parts of tetrahydrofurans, are slowly added dropwise into there-necked flask, and the reaction was continued 3 hours after being added dropwise, reaction knot
The triethylamine hydrochloride of generation is filtered to remove after beam, filtrate washes 3 times, organic solvent is removed under reduced pressure, obtains three (dimethyl-silicons
Base) borate.
(b) there-necked flask matches constant pressure funnel, under 80 DEG C and nitrogen atmosphere, by three (diformazan obtained in step (a)
Base silicon substrate) 50 parts of borate, 50 parts, 0.05 part platiniferous 2% of toluene isopropyl alcohol solution of chloroplatinic acid be added in there-necked flask, then
75 parts of allyl glycidyl ethers, 30 parts of toluene are added in constant pressure funnel, are then slowly dropped in there-necked flask, drop
The reaction was continued after adding 4 hours, and 1 part of active carbon is added after reaction and stirs 0.5 hour, filtering, and solvent and low is evaporated off
Object is boiled, borosilicate modified epoxy is obtained.
The ultraviolet-curing paint the preparation method is as follows: each component is added in container according to parts by weight,
Then container is put into baking oven and increases temperature to 55 DEG C, heated 30 minutes, then take out high-speed stirred dispersion 0.5 hour, so
Ultrasonic disperse 0.5 hour afterwards obtains epoxy ultraviolet-curing paint.
Embodiment 2
A kind of epoxy ultraviolet-curing paint, it is composed of the following components according to parts by weight: bisphenol A type epoxy resin 80
Part, 26 parts of bisphenol-A epoxy resin, 30 parts of borosilicate modified epoxy, 35 parts of glycerin triglycidyl ether, ethyoxyl
Change 15 parts of trimethylolpropane trimethacrylate, 8 parts of triaryl matte hexafluoro antimonate, 2 parts of azodiisobutyronitrile, benzoin isobutyl
2 parts of propyl ether, 5 parts of fluorinated acrylate levelling agent.
The borosilicate modified epoxy the preparation method is as follows:
(a) there-necked flask takes 10 parts of boric acid, 52 under 0 DEG C and nitrogen atmosphere with constant pressure funnel according to parts by weight
Part triethylamine, 50 parts of anhydrous ethers are added in there-necked flask and are sufficiently stirred, and 50 parts of diformazans are then added in constant pressure funnel
Base chlorosilane and 50 parts of anhydrous ethers, are slowly added dropwise into there-necked flask, and the reaction was continued 5 hours after being added dropwise, and reaction terminates
It is filtered to remove the triethylamine hydrochloride of generation afterwards, filtrate washes 3 times, organic solvent is removed under reduced pressure, obtains three (dimethyl silicon substrates)
Borate.
(b) there-necked flask matches constant pressure funnel, under 100 DEG C and nitrogen atmosphere, by three (two obtained in step (a)
Methylsilyl) 50 parts of borate, 50 parts, 0.2 part platiniferous 2% of toluene Karst catalyst be added in there-necked flask, then exist
80 parts of allyl glycidyl ethers, 30 parts of toluene are added in constant pressure funnel, are then slowly dropped in there-necked flask, knot is added dropwise
The reaction was continued after beam 6 hours, and 3 parts of active carbons are added after reaction and stir 2 hours, filtering is evaporated off solvent and low-boiling-point substance, obtains
To borosilicate modified epoxy.
The ultraviolet-curing paint coating the preparation method is as follows: each component is added to container according to parts by weight
In, then container is put into baking oven and increases temperature to 65 DEG C, is heated 90 minutes, then takes out high-speed stirred dispersion 3 hours, so
Ultrasonic disperse 2 hours afterwards obtain epoxy ultraviolet-curing paint.
Embodiment 3
A kind of epoxy ultraviolet-curing paint, it is composed of the following components according to parts by weight: bisphenol A type epoxy resin 65
Part, 18 parts of bisphenol-A epoxy resin, 20 parts of borosilicate modified epoxy, 25 parts of glycerin triglycidyl ether, ethyoxyl
Change 5 parts of trimethylolpropane trimethacrylate, 5 parts of triaryl matte hexafluoro antimonate, 1 part of azodiisobutyronitrile, benzoin isobutyl
1 part of propyl ether, 2 parts of fluorinated acrylate levelling agent.
The borosilicate modified epoxy the preparation method is as follows:
(a) there-necked flask match constant pressure funnel, under -10 DEG C and nitrogen atmosphere, take according to parts by weight 10 parts of boric acid,
50 parts of triethylamines, 50 parts of methylene chloride are added in there-necked flask and are sufficiently stirred, and 47 part two is then added in constant pressure funnel
Methylchlorosilane and 50 parts of methylene chloride, are slowly added dropwise into there-necked flask, and the reaction was continued 4 hours after being added dropwise, reaction knot
The triethylamine hydrochloride of generation is filtered to remove after beam, filtrate washes 3 times, organic solvent is removed under reduced pressure, obtains three (dimethyl-silicons
Base) borate.
(b) there-necked flask matches constant pressure funnel, under 95 DEG C and nitrogen atmosphere, by three (diformazan obtained in step (a)
Base silicon substrate) 50 parts of borate, 50 parts, 0.1 part platiniferous 2% of toluene Karst catalyst be added in there-necked flask, then in perseverance
It presses and 75 parts of allyl glycidyl ethers, 30 parts of toluene is added in dropping funel, be then slowly dropped in there-necked flask, completion of dropwise addition
The reaction was continued afterwards 5 hours, and 2 parts of active carbons are added after reaction and stir 1 hour, filtering is evaporated off solvent and low-boiling-point substance, obtains
Borosilicate modified epoxy.
The ultraviolet-curing paint the preparation method is as follows: each component is added in container according to parts by weight,
Then container is put into baking oven and increases temperature to 60 DEG C, heated 60 minutes, then take out high-speed stirred dispersion 2 hours, then
Ultrasonic disperse 1 hour, obtain epoxy ultraviolet-curing paint.
Embodiment 4
A kind of epoxy ultraviolet-curing paint, it is composed of the following components according to parts by weight: bisphenol A type epoxy resin 75
Part, 25 parts of bisphenol-A epoxy resin, 30 parts of borosilicate modified epoxy, 30 parts of glycerin triglycidyl ether, ethyoxyl
Change 12 parts of trimethylolpropane trimethacrylate, 8 parts of triaryl matte hexafluoro antimonate, 2 parts of azodiisobutyronitrile, benzoin isobutyl
2 parts of propyl ether, 5 parts of fluorinated acrylate levelling agent.
The borosilicate modified epoxy the preparation method is as follows:
(a) there-necked flask match constant pressure funnel, under -5 DEG C and nitrogen atmosphere, take according to parts by weight 10 parts of boric acid,
48 parts of triethylamines, 50 parts there is n-hexane to be added in there-necked flask to be sufficiently stirred, 48 part two is then added in constant pressure funnel
Methylchlorosilane and 50 parts of n-hexanes, are slowly added dropwise into there-necked flask, and the reaction was continued 3 hours after being added dropwise, and reaction terminates
It is filtered to remove the triethylamine hydrochloride of generation afterwards, filtrate washes 3 times, organic solvent is removed under reduced pressure, obtains three (dimethyl silicon substrates)
Borate.
(b) there-necked flask matches constant pressure funnel, under 85 DEG C and nitrogen atmosphere, by three (diformazan obtained in step (a)
Base silicon substrate) 50 parts of borate, 50 parts, 0.15 part platiniferous 2% of toluene allyl silicon (oxygen) alkane platinum complex be added to there-necked flask
In, 80 parts of allyl glycidyl ethers, 30 parts of toluene are then added in constant pressure funnel, are then slowly dropped to there-necked flask
In, the reaction was continued after completion of dropwise addition 4 hours, and 1.5 parts of active carbons are added after reaction and stir 0.5 hour, solvent is evaporated off in filtering
And low-boiling-point substance, obtain borosilicate modified epoxy.
The ultraviolet-curing paint the preparation method is as follows: each component is added in container according to parts by weight,
Then container is put into baking oven and increases temperature to 65 DEG C, heated 30 minutes, then take out high-speed stirred dispersion 0.5 hour, so
Ultrasonic disperse 2 hours afterwards obtain epoxy ultraviolet-curing paint.
Embodiment 5
A kind of epoxy ultraviolet-curing paint, it is composed of the following components according to parts by weight: bisphenol A type epoxy resin 70
Part, 22 parts of bisphenol-A epoxy resin, 28 parts of borosilicate modified epoxy, 30 parts of glycerin triglycidyl ether, ethyoxyl
Change 10 parts of trimethylolpropane trimethacrylate, 6 parts of triaryl matte hexafluoro antimonate, 2 parts of azodiisobutyronitrile, benzoin isobutyl
2 parts of propyl ether, 4 parts of fluorinated acrylate levelling agent.
The borosilicate modified epoxy the preparation method is as follows:
(a) there-necked flask match constant pressure funnel, under -20 DEG C and nitrogen atmosphere, take according to parts by weight 10 parts of boric acid,
48 parts of triethylamines, 50 parts of anhydrous ethers are added in there-necked flask and are sufficiently stirred, and 50 part two is then added in constant pressure funnel
Methylchlorosilane and 50 parts of anhydrous ethers, are slowly added dropwise into there-necked flask, and the reaction was continued 3-5 hours after being added dropwise, reaction
After be filtered to remove the triethylamine hydrochloride of generation, filtrate washes 3 times, organic solvent is removed under reduced pressure, obtains three (dimethyl-silicons
Base) borate.
(b) there-necked flask matches constant pressure funnel, under 100 DEG C and nitrogen atmosphere, by three (two obtained in step (a)
Methylsilyl) 50 parts of borate, 50 parts, 0.2 part platiniferous 2% of toluene Karst catalyst be added in there-necked flask, then exist
75 parts of allyl glycidyl ethers, 30 parts of toluene are added in constant pressure funnel, are then slowly dropped in there-necked flask, knot is added dropwise
The reaction was continued after beam 4 hours, and 3 parts of active carbons are added after reaction and stir 2 hours, filtering is evaporated off solvent and low-boiling-point substance, obtains
To borosilicate modified epoxy.
The ultraviolet-curing paint coating the preparation method is as follows: each component is added to container according to parts by weight
In, then container is put into baking oven and increases temperature to 60 DEG C, is heated 45 minutes, then takes out high-speed stirred dispersion 3 hours, so
Ultrasonic disperse 1.5 hours afterwards obtain epoxy ultraviolet-curing paint.
Performance test
The resin combination of embodiment 1-5 is passed through into photocuring, the film after photocuring passes through performance evaluation, specific item
Part is as follows, the result is as follows:
Pencil hardness: pencil hardness test is by standard GB/T/T6739-2006 test, and bear a heavy burden 500g
Glass transition temperature: DSC temperature range is 20-180 DEG C, 5 DEG C/min of heating rate.
Thermal decomposition temperature: TGA temperature range is 50-800 DEG C, 10 DEG C/min of heating rate.
Surface contact angle: GB/T23764-2009 standard testing is pressed in water contact angle test.
Cubical contraction: the measurement work formula of cubical contraction is as follows
Wherein, η is that resin UV solidifies front and back cubical contraction, ρsFor the density for solidifying exemplar, ρlTo solidify preceding resin liquid
Density.
Water absorption rate: after the resin after the completion of solidification is placed in 100 DEG C of oven drying 5h, its weight m is surveyed0, then by batten
It is vertically arranged in the beaker for filling distilled water, distilled water liquid level is higher than batten, and removes the bubble on print.After 7 days, sample is taken out
Piece surveys its weight m after drying moisture1。