CN108047893A - A kind of environmental protection ultraviolet-curing paint - Google Patents
A kind of environmental protection ultraviolet-curing paint Download PDFInfo
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- CN108047893A CN108047893A CN201711245433.3A CN201711245433A CN108047893A CN 108047893 A CN108047893 A CN 108047893A CN 201711245433 A CN201711245433 A CN 201711245433A CN 108047893 A CN108047893 A CN 108047893A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of environmentally friendly ultraviolet-curing paint, it is characterized in that, it counts in parts by weight composed of the following components：60 80 parts of epoxy acrylic, 50 65 parts of epoxy acrylate diluent, 20 45 parts of glycidyl acrylic resin, 20 30 parts of modifying epoxy resin by organosilicon, 20 35 parts of polyurethane acroleic acid oligomer, 60 80 parts of trimethylolpropane trimethacrylate, 5 15 parts of ethoxylated trimethylolpropane triacrylate, 2,4,6（Trimethylbenzoyl）58 parts of diphenyl phosphine oxide, 13 parts of 1 hydroxy-cyclohexyl, one phenyl ketone, 0.5 1.5 parts of triaryl matte hexafluoro antimonate.The present invention has the advantages that：（1）The fast completion of cure of resin solidification speed；（2））Resin system viscosity is relatively low；（3））Hardness of film height, high and low temperature resistance and good toughness after curing.
Description
Technical field
The present invention relates to a kind of coating, more particularly, to a kind of environmentally friendly ultraviolet-curing paint.
Background technology
In the past few years, ultraviolet-curing paint fibre coating, CD coatings/DVD adhesives, credit card, timber,
It suffers from very rapidly developing in beverage can, food packaging, journal surface, medical instrument and automobile industry.Ultraviolet light cures
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.It is to cause light by radiation that ultraviolet light, which cures cured key reaction course,
Decomposition of initiator, generation living radical trigger monomer/oligomer polymerization crosslinking.
The resin that ultraviolet light uses in curing at present is just two kinds of substantially acrylic resin and epoxy resin, wherein third
Olefin(e) acid resin is the resin made of esters of acrylic acid and methyl acrylic ester and other olefinic type monomers are copolymerized, passes through selection
Different resin structure, different formulas, production technology and solvent compositions, can synthesize different type, different performance and difference should
With the acrylic resin of occasion, acrylic resin can be divided into thermoplastic acrylic resin again according to structure and the difference of membrane formation mechanism
And thermosetting acrylic resin.With main suction of the acrylic resin of acrylate and methacrylate monomers copolymerization to light
It receives peak to be in outside solar spectrum scope, so acrylic resin paint obtained has excellent light resistance and anti-outdoor aging
Energy.Thermosetting acrylic resin refers in the structure with certain functional group, in painting by amino resins with addition,
Functional group reactions in epoxy resin, polyurethane etc. form net structure, and the general relative molecular weight of thermosetting resin is relatively low.Thermosetting
Property acrylic coating have excellent richness, gloss, hardness, solvent resistance, weatherability, in high-temperature baking it is non-discolouring, do not return
It is yellow.Most important application be with amino resins cooperation amino-acrylonitrile acid baking vanish is made, at present automobile, motorcycle, bicycle,
Using very extensive on the products such as coil.
However the energy at present used in acrylate ultraviolet light curable coating photocuring on the market is higher, is obtained after curing
Although film hardness it is higher, it is more crisp, can not impact resistance, high and low temperature resistance, and it is not water-fast intolerant to dirt.It is such as a kind of
A kind of light-cured resin reported in Chinese patent literature and application thereof, application publication number are 106866889 A of CN, should
Light-cured resin is made of based on mass percentage following component：Ethyl methacrylate is 4.6-10.8%, ethyl acetate
It is 0.1-0.6% for 4.6-9.2%, polyurethane acrylic resin 80-90%, benzophenone -1.The light-cured resin of the present invention
Cost of material is cheap, and it is convenient to obtain, and is easy to store, nontoxic to human body, drops in good penetrability on fiber, and film forming rapidly may be used
Control, solid flexible, section is easy to operate, and success rate is high, and the fiber cross section cut out clearly easily distinguishes that the extruding of fiber is smaller,
Fiber degree of scatter is high, and border and lumen are clear, and feature is apparent, are easy to differentiate.But it is there is also more deficiency, such as it makes
It is mostly small molecule acrylate, after photocuring, crosslink density is larger, although with preferable hardness, toughness
It is not high, and its high and low temperature resistance is poor can not meet daily use.
The content 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 curing compared with
It is crisp, provide one kind can high-low temperature resistant, a kind of tough and tensile environmentally friendly ultraviolet-curing paint of the coating property that is obtained after curing.
To achieve these goals, the present invention uses following technical scheme：
A kind of environmental protection ultraviolet-curing paint, is counted composed of the following components in parts by weight：60-80 parts of epoxy acrylic, epoxy
50-65 parts of acrylate diluent, 20-45 parts of glycidyl acrylic resin, 20-30 parts of modifying epoxy resin by organosilicon,
20-35 parts of polyurethane acroleic acid oligomer, 60-80 parts of trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane
5-15 parts of triacrylate, 5-8 parts of 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, one phenyl first of 1- hydroxy-cyciohexyls
1-3 parts of ketone, 0.5-1.5 parts of triaryl matte hexafluoro antimonate.
Preferably, it counts in parts by weight composed of the following components：65-75 parts of epoxy acrylic, epoxy acrylate are dilute
Release 55-60 parts of agent, 25-40 parts of glycidyl acrylic resin, 22-28 parts of modifying epoxy resin by organosilicon, polyurethane propylene
25-30 parts of acid oligomer, 65-75 parts of trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate
5-15 parts, 5-8 parts of 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, 1-3 parts of one phenyl ketone of 1- hydroxy-cyciohexyls, three
0.5-1.5 parts of aryl sulfonium hexafluoro antimonate.
Preferably, it counts in parts by weight composed of the following components：70 parts of epoxy acrylic, epoxy acrylate diluent
58 parts, 30 parts of glycidyl acrylic resin, 25 parts of modifying epoxy resin by organosilicon, 28 parts of polyurethane acroleic acid oligomer,
70 parts of trimethylolpropane trimethacrylate, 7 parts of ethoxylated trimethylolpropane triacrylate, 2,4,6 (trimethylbenzene first
Acyl group) 7 parts of diphenyl phosphine oxide, 2 parts of one phenyl ketone of 1- hydroxy-cyciohexyls, 1 part of triaryl matte hexafluoro antimonate.
The longer acrylic monomers and epoxy monomer of segment is selected in the present invention, be used in conjunction with each other both ensure that it is original
Intensity and hardness, and improve the final toughness for being formed by curing object.Trimethylolpropane trimethacrylate, propylene oxide simultaneously
The addition of the low viscosity resins such as acid esters diluent, ethoxylated trimethylolpropane triacrylate can effectively reduce system
Overall viscosity contributes to the filming performance of resin.Further, since modifying epoxy resin by organosilicon in its main chain due to containing Si-
O-Si structures, high and low temperature resistance is superior, is capable of the high and low temperature resistance of reinforced resin material.2,4,6 (trimethylbenzoyls
Base) diphenyl phosphine oxide, one phenyl ketone of 1- hydroxy-cyciohexyls, the different initiators of three kinds of triaryl matte hexafluoro antimonate it
Between cooperate, the efficiency of initiation of photocuring can be greatly improved, ensure that acrylic resin can be complete with epoxy resin
Cure, moreover it is possible to reduce the solidification energy of photocuring.
Preferably, the preparation method of the modifying epoxy resin by organosilicon is as follows：
(a) there-necked flask matches somebody with somebody constant pressure funnel, and under -20-0 DEG C and nitrogen atmosphere, 10 parts of diphenyl are taken according to parts by weight
Silicon diol, 48-52 part triethylamine, 50 parts of tetrahydrofurans are added in reaction kettle and are sufficiently stirred, then in the low liquid funnel of constant pressure
3-6 part dimethylchlorosilanes and 50 parts of tetrahydrofurans are added in, are slowly added dropwise into there-necked flask, the 3- that is added dropwise that the reaction was continued afterwards
5 it is small when, be filtered to remove the triethylamine hydrochloride of generation after reaction, filtrate washes 3 times, tetrahydrofuran is removed under reduced pressure, obtains
3,3- diphenyl -1,1,5,5- tetramethyl trisiloxanes.
(b) there-necked flask matches somebody with somebody constant pressure funnel, under 80-100 DEG C and atmosphere, 3, the 3- bis- that will be obtained in step (a)
Phenyl -1,1,5,5- 50 parts of tetramethyl trisiloxanes, the Karst catalyst of 50 parts, 0.05-0.2 parts platiniferous 2% of toluene, then
75-80 parts of allyl glycidyl ethers, 30 parts of toluene are added in constant pressure funnel, is then slowly dropped to constant pressure addition leakage
When bucket, the reaction was continued after completion of dropwise addition 4-6 are small, add in after reaction 1-3 part activated carbons stirring 0.5-2 it is small when, filter, be evaporated off
Solvent and low-boiling-point substance, obtain modifying epoxy resin by organosilicon.
Preferably, the preparation method of the ultraviolet-curing paint coating is as follows：By epoxy acrylic, propylene oxide
Acid esters diluent, glycidyl acrylic resin, modifying epoxy resin by organosilicon, polyurethane acroleic acid oligomer, three hydroxyl first
Base propane triacrylate and ethoxylated trimethylolpropane triacrylate are added to according to parts by weight in container, so
Container is put into baking oven afterwards and raises temperature to 45 DEG C, is heated 30-90 minutes, is then taken out, add 2,4,6 (trimethylbenzenes
Formoxyl) diphenyl phosphine oxide, one phenyl ketone of 1- hydroxy-cyciohexyls and triaryl matte hexafluoro antimonate, high-speed stirred
When scattered 0.5-3 is small, when then ultrasonic disperse 0.5-2 is small, finally with vacuum drying chamber deaeration, it is kept in dark place to obtain UV light
Change coating.
Therefore, the present invention has the advantages that：(1) the fast completion of cure of resin solidification speed；(2)) resin system glues
It spends relatively low；(3)) hardness of film height, high and low temperature resistance and good toughness after curing.
Technical scheme is made below by specific embodiment to further describe explanation.
If without specified otherwise, the raw material that use is said in the embodiment of the present invention is raw material commonly used in the art, is implemented
Method employed in example is the conventional method of this field.
Embodiment 1
A kind of environmental protection ultraviolet-curing paint, is counted composed of the following components in parts by weight：60 parts of epoxy acrylic, propylene oxide
50 parts of acid esters diluent, 20 parts of glycidyl acrylic resin, 20 parts of modifying epoxy resin by organosilicon, polyurethane acroleic acid are low
20 parts of polymers, 60 parts of trimethylolpropane trimethacrylate, 5 parts of ethoxylated trimethylolpropane triacrylate, 2,4,6
5 parts of (trimethylbenzoyl) diphenyl phosphine oxide, 1 part of one phenyl ketone of 1- hydroxy-cyciohexyls, triaryl matte hexafluoro-antimonic acid
0.5 part of salt.
The preparation method of the modifying epoxy resin by organosilicon is as follows：
(a) there-necked flask matches somebody with somebody constant pressure funnel, and under -20 DEG C and nitrogen atmosphere, 10 parts of diphenyl silicon are taken according to parts by weight
Glycol, 48 parts of triethylamines, 50 parts of tetrahydrofurans are added in reaction kettle and are sufficiently stirred, and then add in 45 in the low liquid funnel of constant pressure
Part dimethylchlorosilane and 50 parts of tetrahydrofurans, are slowly added dropwise into there-necked flask, be added dropwise that the reaction was continued afterwards 3 it is small when, instead
The triethylamine hydrochloride of generation is filtered to remove after answering, filtrate washes 3 times, tetrahydrofuran is removed under reduced pressure, obtains 3,3- hexichol
Base -1,1,5,5- tetramethyl trisiloxanes.
(b) there-necked flask match somebody with somebody constant pressure funnel, under 80 DEG C and atmosphere, by 3, the 3- diphenyl obtained in step (a)-
Then the Karst catalyst of 50 parts, 0.05 part 1,1,5,5- 50 parts of tetramethyl trisiloxanes, toluene platiniferous 2% is dripped in constant pressure
75 parts of allyl glycidyl ethers, 30 parts of toluene are added in liquid funnel, is then slowly dropped to constant pressure funnel, completion of dropwise addition
The reaction was continued afterwards 4 it is small when, add in after reaction 1 part of activated carbon stirring 0.5 it is small when, filtering is evaporated off solvent and low-boiling-point substance, obtains
To modifying epoxy resin by organosilicon.
The preparation method of the ultraviolet-curing paint coating is as follows：Epoxy acrylic, epoxy acrylate are diluted
Agent, glycidyl acrylic resin, modifying epoxy resin by organosilicon, polyurethane acroleic acid oligomer, trimethylolpropane tris
Acrylate and ethoxylated trimethylolpropane triacrylate are added to according to parts by weight in container, then by container
It is put into baking oven and raises temperature to 45 DEG C, heat 30 minutes, then take out, add 2,4,6 (trimethylbenzoyl) hexichol
Base phosphine oxide, one phenyl ketone of 1- hydroxy-cyciohexyls and triaryl matte hexafluoro antimonate, high-speed stirred disperse 0.5 it is small when,
Then when ultrasonic disperse 0.5 is small, finally with vacuum drying chamber deaeration, it is kept in dark place to obtain ultraviolet-curing paint.
Embodiment 2
A kind of environmental protection ultraviolet-curing paint, is counted composed of the following components in parts by weight：80 parts of epoxy acrylic, propylene oxide
65 parts of acid esters diluent, 45 parts of glycidyl acrylic resin, 30 parts of modifying epoxy resin by organosilicon, polyurethane acroleic acid are low
35 parts of polymers, 80 parts of trimethylolpropane trimethacrylate, 15 parts of ethoxylated trimethylolpropane triacrylate, 2,4,6
8 parts of (trimethylbenzoyl) diphenyl phosphine oxide, 3 parts of one phenyl ketone of 1- hydroxy-cyciohexyls, triaryl matte hexafluoro-antimonic acid
1.5 parts of salt.
(a) there-necked flask matches somebody with somebody constant pressure funnel, and under 0 DEG C and nitrogen atmosphere, 10 parts of diphenyl are taken according to parts by weight
Silicon diol, 52 parts of triethylamines, 50 parts of tetrahydrofurans are added in reaction kettle and are sufficiently stirred, and are then added in the low liquid funnel of constant pressure
50 parts of dimethylchlorosilanes and 50 parts of anhydrous ethers, are slowly added dropwise into there-necked flask, be added dropwise after the reaction was continued 5 it is small when,
The triethylamine hydrochloride of generation is filtered to remove after reaction, and filtrate washes 3 times, tetrahydrofuran is removed under reduced pressure, obtains 3,3- bis-
Phenyl -1,1,5,5- tetramethyl trisiloxanes.
(b) there-necked flask matches somebody with somebody constant pressure funnel, under 100 DEG C and atmosphere, 3, the 3- hexichol that will be obtained in step (a)
Base -1,1,5,5- 50 parts of tetramethyl trisiloxanes, the Karst catalyst of 50 parts, 0.2 part platiniferous 2% of toluene, then in constant pressure
80 parts of allyl glycidyl ethers, 30 parts of toluene are added in dropping funel, is then slowly dropped to constant pressure funnel, knot is added dropwise
The reaction was continued after beam 6 it is small when, add in after reaction 3 parts of activated carbons stirring 2 it is small when, filtering is evaporated off solvent and low-boiling-point substance, obtains
To modifying epoxy resin by organosilicon.
The preparation method of the ultraviolet-curing paint coating is as follows：Epoxy acrylic, epoxy acrylate are diluted
Agent, glycidyl acrylic resin, modifying epoxy resin by organosilicon, polyurethane acroleic acid oligomer, trimethylolpropane tris
Acrylate and ethoxylated trimethylolpropane triacrylate are added to according to parts by weight in container, then by container
It is put into baking oven and raises temperature to 45 DEG C, heat 90 minutes, then take out, add 2,4,6 (trimethylbenzoyl) hexichol
Base phosphine oxide, one phenyl ketone of 1- hydroxy-cyciohexyls and triaryl matte hexafluoro antimonate, high-speed stirred disperse 3 it is small when, so
When ultrasonic disperse 2 is small afterwards, finally with vacuum drying chamber deaeration, it is kept in dark place to obtain ultraviolet-curing paint.
Embodiment 3
A kind of environmental protection ultraviolet-curing paint, is counted composed of the following components in parts by weight：65 parts of epoxy acrylic, propylene oxide
55 parts of acid esters diluent, 25 parts of glycidyl acrylic resin, 22 parts of modifying epoxy resin by organosilicon, polyurethane acroleic acid are low
25 parts of polymers, 65 parts of trimethylolpropane trimethacrylate, 5 parts of ethoxylated trimethylolpropane triacrylate, 2,4,6
6 parts of (trimethylbenzoyl) diphenyl phosphine oxide, 2 parts of one phenyl ketone of 1- hydroxy-cyciohexyls, triaryl matte hexafluoro-antimonic acid
1 part of salt.
The preparation method of the modifying epoxy resin by organosilicon is as follows：
(a) there-necked flask matches somebody with somebody constant pressure funnel, and under -10 DEG C and nitrogen atmosphere, 10 parts of diphenyl silicon are taken according to parts by weight
Glycol, 50 parts of triethylamines, 50 parts of dichloromethane are added in reaction kettle and are sufficiently stirred, and then add in 47 in the low liquid funnel of constant pressure
Part dimethylchlorosilane and 50 parts of tetrahydrofurans, are slowly added dropwise into there-necked flask, be added dropwise that the reaction was continued afterwards 4 it is small when, instead
The triethylamine hydrochloride of generation is filtered to remove after answering, filtrate washes 3 times, tetrahydrofuran is removed under reduced pressure, obtains 3,3- hexichol
Base -1,1,5,5- tetramethyl trisiloxanes.
(b) there-necked flask match somebody with somebody constant pressure funnel, under 95 DEG C and atmosphere, by 3, the 3- diphenyl obtained in step (a)-
The Karst catalyst of 50 parts, 0.1 part 1,1,5,5- 50 parts of tetramethyl trisiloxanes, toluene platiniferous 2%, then in constant pressure addition
75 parts of allyl glycidyl ethers, 30 parts of toluene are added in funnel, constant pressure funnel is then slowly dropped to, after completion of dropwise addition
The reaction was continued 5 it is small when, add in after reaction 2 parts of activated carbons stirring 1 it is small when, filtering is evaporated off solvent and low-boiling-point substance, is had
Machine silicon modified epoxy resin.
The preparation method of the ultraviolet-curing paint coating is as follows：Epoxy acrylic, epoxy acrylate are diluted
Agent, glycidyl acrylic resin, modifying epoxy resin by organosilicon, polyurethane acroleic acid oligomer, trimethylolpropane tris
Acrylate and ethoxylated trimethylolpropane triacrylate are added to according to parts by weight in container, then by container
It is put into baking oven and raises temperature to 45 DEG C, heat 50 minutes, then take out, add 2,4,6 (trimethylbenzoyl) hexichol
Base phosphine oxide, one phenyl ketone of 1- hydroxy-cyciohexyls and triaryl matte hexafluoro antimonate, high-speed stirred disperse 2 it is small when, so
When ultrasonic disperse 1 is small afterwards, finally with vacuum drying chamber deaeration, it is kept in dark place to obtain ultraviolet-curing paint.
Embodiment 4
A kind of environmental protection ultraviolet-curing paint, is counted composed of the following components in parts by weight：75 parts of epoxy acrylic, propylene oxide
60 parts of acid esters diluent, 40 parts of glycidyl acrylic resin, 28 parts of modifying epoxy resin by organosilicon, polyurethane acroleic acid are low
30 parts of polymers, 75 parts of trimethylolpropane trimethacrylate, 15 parts of ethoxylated trimethylolpropane triacrylate, 2,4,6
5 parts of (trimethylbenzoyl) diphenyl phosphine oxide, 3 parts of one phenyl ketone of 1- hydroxy-cyciohexyls, triaryl matte hexafluoro-antimonic acid
1.5 parts of salt.
The preparation method of the modifying epoxy resin by organosilicon is as follows：
(a) there-necked flask matches somebody with somebody constant pressure funnel, and under -5 DEG C and nitrogen atmosphere, 10 parts of diphenyl silicon two are taken according to parts by weight
Alcohol, 48 parts of triethylamines, 50 parts there is n-hexane to be added in reaction kettle to be sufficiently stirred, 48 parts are then added in the low liquid funnel of constant pressure
Dimethylchlorosilane and 50 parts of tetrahydrofurans, are slowly added dropwise into there-necked flask, be added dropwise after the reaction was continued 3 it is small when, reaction
After be filtered to remove the triethylamine hydrochloride of generation, filtrate is washed 3 times, and tetrahydrofuran is removed under reduced pressure, obtain 3,3- diphenyl-
1,1,5,5- tetramethyl trisiloxanes.
(b) there-necked flask match somebody with somebody constant pressure funnel, under 85 DEG C and atmosphere, by 3, the 3- diphenyl obtained in step (a)-
Then the Karst catalyst of 50 parts, 0.15 part 1,1,5,5- 50 parts of tetramethyl trisiloxanes, toluene platiniferous 2% is dripped in constant pressure
80 parts of allyl glycidyl ethers, 30 parts of toluene are added in liquid funnel, is then slowly dropped to constant pressure funnel, completion of dropwise addition
The reaction was continued afterwards 4 it is small when, add in after reaction 1.5 parts of activated carbons stirring 0.5 it is small when, solvent and low-boiling-point substance is evaporated off in filtering,
Obtain modifying epoxy resin by organosilicon.
The preparation method of the ultraviolet-curing paint coating is as follows：Epoxy acrylic, epoxy acrylate are diluted
Agent, glycidyl acrylic resin, modifying epoxy resin by organosilicon, polyurethane acroleic acid oligomer, trimethylolpropane tris
Acrylate and ethoxylated trimethylolpropane triacrylate are added to according to parts by weight in container, then by container
It is put into baking oven and raises temperature to 45 DEG C, heat 60 minutes, then take out, add 2,4,6 (trimethylbenzoyl) hexichol
Base phosphine oxide, one phenyl ketone of 1- hydroxy-cyciohexyls and triaryl matte hexafluoro antimonate, high-speed stirred disperse 1 it is small when, so
When ultrasonic disperse 2 is small afterwards, finally with vacuum drying chamber deaeration, it is kept in dark place to obtain ultraviolet-curing paint.
Embodiment 5
A kind of environmental protection ultraviolet-curing paint, is counted composed of the following components in parts by weight：70 parts of epoxy acrylic, propylene oxide
58 parts of acid esters diluent, 30 parts of glycidyl acrylic resin, 25 parts of modifying epoxy resin by organosilicon, polyurethane acroleic acid are low
28 parts of polymers, 70 parts of trimethylolpropane trimethacrylate, 7 parts of ethoxylated trimethylolpropane triacrylate, 2,4,6
7 parts of (trimethylbenzoyl) diphenyl phosphine oxide, 2 parts of one phenyl ketone of 1- hydroxy-cyciohexyls, triaryl matte hexafluoro-antimonic acid
1 part of salt.
The preparation method of the modifying epoxy resin by organosilicon is as follows：
(a) there-necked flask matches somebody with somebody constant pressure funnel, and under -20 DEG C and nitrogen atmosphere, 10 parts of diphenyl silicon are taken according to parts by weight
Glycol, 48 parts of triethylamines, 50 parts of tetrahydrofurans are added in reaction kettle and are sufficiently stirred, and then add in 50 in the low liquid funnel of constant pressure
Part dimethylchlorosilane and 50 parts of anhydrous ethers, are slowly added dropwise into there-necked flask, when the 3-5 that is added dropwise that the reaction was continued afterwards is small,
The triethylamine hydrochloride of generation is filtered to remove after reaction, and filtrate washes 3 times, tetrahydrofuran is removed under reduced pressure, obtains 3,3- bis-
Phenyl -1,1,5,5- tetramethyl trisiloxanes.
(b) there-necked flask matches somebody with somebody constant pressure funnel, under 100 DEG C and atmosphere, 3, the 3- hexichol that will be obtained in step (a)
Base -1,1,5,5- 50 parts of tetramethyl trisiloxanes, the Karst catalyst of 50 parts, 0.2 part platiniferous 2% of toluene, then in constant pressure
75 parts of allyl glycidyl ethers, 30 parts of toluene are added in dropping funel, is then slowly dropped to constant pressure funnel, knot is added dropwise
The reaction was continued after beam 4 it is small when, add in after reaction 3 parts of activated carbons stirring 2 it is small when, filtering is evaporated off solvent and low-boiling-point substance, obtains
To modifying epoxy resin by organosilicon.
The preparation method of the ultraviolet-curing paint coating is as follows：Epoxy acrylic, epoxy acrylate are diluted
Agent, glycidyl acrylic resin, modifying epoxy resin by organosilicon, polyurethane acroleic acid oligomer, trimethylolpropane tris
Acrylate and ethoxylated trimethylolpropane triacrylate are added to according to parts by weight in container, then by container
It is put into baking oven and raises temperature to 45 DEG C, heat 60 minutes, then take out, add 2,4,6 (trimethylbenzoyl) hexichol
Base phosphine oxide, one phenyl ketone of 1- hydroxy-cyciohexyls and triaryl matte hexafluoro antimonate, high-speed stirred disperse 3 it is small when, so
When ultrasonic disperse 1 is small afterwards, finally with vacuum drying chamber deaeration, it is kept in dark place to obtain ultraviolet-curing paint.
Performance test
By the resin combination of embodiment 1-5 by photocuring, the film after photocuring is by performance evaluation, and actual conditions is such as
Under, result such as following table：
Pencil hardness：Pencil hardness test is by standard GB/T/T6739-2006 tests, heavy burden 500g
Glass transition temperature：It is 20-180 DEG C to set DSC temperature ranges, 5 DEG C/min of heating rate.
Viscosity test：Using the NDJ-7 type rotational viscometers of Shanghai balance equipment factory, control loop coolant-temperature gage at 30 DEG C,
Measure the viscosity of resin sample to be measured at 30 DEG C.
Heat decomposition temperature：It is 50-800 DEG C to set TGA temperature ranges, 10 DEG C/min of heating rate.
Cubical contraction：The measure work formula of cubical contraction is as follows
Wherein, cubical contraction before and after η cures for resin UV, ρsTo cure the density of exemplar, ρ1For resin liquid before curing
Density.
Water absorption rate：After resin after the completion of curing 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。
Claims (6)
1. a kind of environmental protection ultraviolet-curing paint, it is characterized in that, it counts in parts by weight composed of the following components：Epoxy acrylic
60-80 parts, 50-65 parts of epoxy acrylate diluent, 20-45 parts of glycidyl acrylic resin, silicon-modified epoxy
20-30 parts of resin, 20-35 parts of polyurethane acroleic acid oligomer, 60-80 parts of trimethylolpropane trimethacrylate, ethoxylation
5-15 parts of trimethylolpropane trimethacrylate, 2,4,6（Trimethylbenzoyl）5-8 parts of diphenyl phosphine oxide, 1- hydroxyls-ring
1-3 parts of one phenyl ketone of hexyl, 0.5-1.5 parts of triaryl matte hexafluoro antimonate.
2. a kind of environmentally friendly ultraviolet-curing paint according to claim 1, it is characterized in that, it is counted in parts by weight by with the following group
It is grouped into：65-75 parts of epoxy acrylic, 55-60 parts of epoxy acrylate diluent, glycidyl acrylic resin 25-40
Part, 22-28 parts of modifying epoxy resin by organosilicon, 25-30 parts of polyurethane acroleic acid oligomer, trimethylolpropane trimethacrylate
65-75 parts, 5-15 parts of ethoxylated trimethylolpropane triacrylate, 2,4,6（Trimethylbenzoyl）Diphenyl aoxidizes
5-8 parts of phosphine, 1-3 parts of one phenyl ketone of 1- hydroxy-cyciohexyls, 0.5-1.5 parts of triaryl matte hexafluoro antimonate.
3. a kind of environmentally friendly ultraviolet-curing paint according to claim 1, it is characterized in that, it is counted in parts by weight by with the following group
It is grouped into：70 parts of epoxy acrylic, 58 parts of epoxy acrylate diluent, 30 parts of glycidyl acrylic resin, organosilicon
25 parts of modified epoxy, 28 parts of polyurethane acroleic acid oligomer, 70 parts of trimethylolpropane trimethacrylate, ethoxylation three
7 parts of hydroxymethyl-propane triacrylate, 2,4,6（Trimethylbenzoyl）7 parts of diphenyl phosphine oxide, 1- hydroxy-cyciohexyls one
2 parts of phenyl ketone, 1 part of triaryl matte hexafluoro antimonate.
4. a kind of environmentally friendly ultraviolet-curing paint according to claim 1 ~ 3, it is characterized in that, the organic silicon modified epoxy
The preparation method of oxygen resin is as follows：
（a）There-necked flask matches somebody with somebody constant pressure funnel, and under -20-0 DEG C and nitrogen atmosphere, 10 parts of diphenyl are taken according to parts by weight
Silicon diol, 48-52 part triethylamine, 50 parts of tetrahydrofurans are added in reaction kettle and are sufficiently stirred, then in the low liquid funnel of constant pressure
3-6 part dimethylchlorosilanes and 50 parts of tetrahydrofurans are added in, are slowly added dropwise into there-necked flask, the 3- that is added dropwise that the reaction was continued afterwards
5 it is small when, be filtered to remove the triethylamine hydrochloride of generation after reaction, filtrate washes 3 times, tetrahydrofuran is removed under reduced pressure, obtains
3,3- diphenyl -1,1,5,5- tetramethyl trisiloxanes；
（b）There-necked flask matches somebody with somebody constant pressure funnel, under 80-100 DEG C and atmosphere, by step（a）In obtain 3,3- diphenyl-
The Karst catalyst of 50 parts, 0.05-0.2 parts 1,1,5,5- 50 parts of tetramethyl trisiloxanes, toluene platiniferous 2%, then in constant pressure
75-80 parts of allyl glycidyl ethers, 30 parts of toluene are added in dropping funel, is then slowly dropped to constant pressure funnel, is dripped
When the reaction was continued after adding 4-6 is small, add in after reaction 1-3 part activated carbons stirring 0.5-2 it is small when, filter, solvent be evaporated off
And low-boiling-point substance, obtain modifying epoxy resin by organosilicon.
5. a kind of environmentally friendly ultraviolet-curing paint according to claim 4, it is characterized in that, the step（a）In four
Hydrogen furans is tetrahydrofuran, one kind in anhydrous ether, dichloromethane, n-hexane.
6. a kind of environmentally friendly ultraviolet-curing paint according to claim 1 ~ 3, it is characterized in that, the ultraviolet light, which cures, to be applied
Expect that the preparation method of coating is as follows：By epoxy acrylic, epoxy acrylate diluent, glycidyl acrylic resin, have
Machine silicon modified epoxy resin, three hydroxyl first of polyurethane acroleic acid oligomer, trimethylolpropane trimethacrylate and ethoxylation
Base propane triacrylate is added to according to parts by weight in container, and then container is put into baking oven and raises temperature to 45 DEG C,
Heating 30-90 minutes, then takes out, adds 2,4,6（Trimethylbenzoyl）Diphenyl phosphine oxide, 1- hydroxy-cyciohexyls
One phenyl ketone and triaryl matte hexafluoro antimonate, high-speed stirred disperse 0.5-3 it is small when, then ultrasonic disperse 0.5-2 is small
When, finally with vacuum drying chamber deaeration, it is kept in dark place to obtain ultraviolet-curing paint.
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Cited By (1)
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| CN114634756A (en) * | 2022-03-17 | 2022-06-17 | 苏州市三新材料科技股份有限公司 | Hybrid ultraviolet curing coating special for scribing and repairing coating and preparation method and application method thereof |
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Application publication date: 20180518 |