CN116333570A - Ultraviolet light curing coating for polyurethane glass fiber composite material - Google Patents
Ultraviolet light curing coating for polyurethane glass fiber composite material Download PDFInfo
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- CN116333570A CN116333570A CN202310351137.0A CN202310351137A CN116333570A CN 116333570 A CN116333570 A CN 116333570A CN 202310351137 A CN202310351137 A CN 202310351137A CN 116333570 A CN116333570 A CN 116333570A
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- China
- Prior art keywords
- glass fiber
- fiber composite
- composite material
- ultraviolet light
- polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 79
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 78
- 238000000576 coating method Methods 0.000 title claims abstract description 77
- 239000011248 coating agent Substances 0.000 title claims abstract description 75
- 239000003365 glass fiber Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 24
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 239000002518 antifoaming agent Substances 0.000 claims abstract 2
- 125000003700 epoxy group Chemical group 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 11
- -1 acrylic phosphate compound Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012952 cationic photoinitiator Substances 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical group C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- WTRRGIQUWPQIEA-UHFFFAOYSA-N methyl prop-2-enoate propane Chemical compound CCC.COC(C=C)=O WTRRGIQUWPQIEA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 43
- 238000001723 curing Methods 0.000 description 29
- 239000000463 material Substances 0.000 description 11
- 230000006378 damage Effects 0.000 description 10
- 239000011253 protective coating Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 208000027418 Wounds and injury Diseases 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 208000014674 injury Diseases 0.000 description 5
- 239000004843 novolac epoxy resin Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000004224 protection Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012949 free radical photoinitiator Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000036314 physical performance Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
-
- 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
- C09D5/08—Anti-corrosive paints
-
- 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
-
- 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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides an ultraviolet light curing coating for a polyurethane glass fiber composite material, and relates to the technical field of coatings; the coating comprises the following components in parts by weight: 50-70 parts of UV resin; 5-10 parts of UV monomer; 2-5 parts of adhesion promoter; 0.1-0.5 part of anti-settling agent; 0.01-0.1 part of defoaming agent; 15-25 parts of filler; 1.5-3 parts of an initiator; 0.5-0.6 part of wax powder; the UV resin is prepared from phenolic epoxy acrylate oligomer and polyurethane acrylate oligomer according to the mass ratio of (4-5): 1. The ultraviolet light curing coating for the polyurethane glass fiber composite material provided by the invention takes the phenolic epoxy acrylate oligomer and the polyurethane acrylate oligomer as main resins, and the prepared coating has good cold and hot temperature difference resistance, high temperature resistance and corrosion resistance, is beneficial to improving the processing performance of the polyurethane glass fiber composite material and expands the application range of the polyurethane glass fiber composite material.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to an ultraviolet light curing coating for polyurethane glass fiber composite materials.
Background
In recent years, energy saving of buildings has become an important component of sustainable development, and in buildings, doors and windows, outer walls, roofs and floors are four major parts of main energy consumption of the buildings, wherein the heat insulation of the doors and windows is the worst. It is estimated that for typical enclosure components in China, the energy consumption of doors and windows is about 4 times of that of walls, 5 times of that of roofs and 20 times of that of floors, and the energy consumption of the doors and windows is about 40% -50% of that of the enclosure components, so that the enhancement of the heat preservation and insulation performance of doors and windows is an important link for improving the indoor thermal environment quality and the energy saving level of buildings. The composite material is raised in application, and brings new ideas for us, so that the composite material can be possibly applied to reconstruction of energy-saving doors and windows of buildings.
Glass fiber reinforced polyurethane (GRPU) pultruded door and window section is produced by using glass fiber as reinforcing material, polyurethane as matrix and advanced injection dipping pultrusion process. The development of GRPU door and window profile is to provide high-rise building with energy-saving window solution with total heat transfer coefficient K less than or equal to 2.0W/(m.K). Polyurethane (PU) has excellent heat insulation capability, and the advantages of the GRPU window frame are determined by the characteristics of GRPU materials; GRPU as one new kind of composite material can be used in preparing large, thin and strong section bar for large window frame and curtain wall. Meanwhile, the GRPU window frame has excellent expansion and contraction performance, can resist various climatic conditions, and is suitable for various climatic environments from arctic severe cold to desert hot and seaside humid.
Because glass fiber reinforced polyurethane pultrusion door and window profiles are produced by taking glass fiber as a reinforcing material and polyurethane as a matrix through an advanced injection dipping pultrusion process, a lot of glass fibers on the surface of GRPU cause physical injury to deep processing workers, such as great injury to respiratory tract and skin, and are unfavorable for deep processing. In addition, because glass fiber on the GRPU surface is easy to break, the glass fiber is easy to cause surface damage of the section bar in transportation and installation, and the fallen glass fiber can cause harm to the environment and human body, the coating protection on the glass fiber surface is extremely important.
At present, solvent paint is generally used as a protective coating of the polyurethane glass fiber composite material, and the coating prepared by the method has a certain protective effect, but has poor cold and heat temperature difference resistance, and paint film bubbling easily occurs in the use process, so that the service life of the polyurethane glass fiber composite material is influenced.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to solve the problem of poor cold and hot temperature difference resistance of a protective coating of a polyurethane glass fiber composite material in the prior art, the invention provides an ultraviolet light curing coating for the polyurethane glass fiber composite material, which is a system formed by UV resin, a monomer and other auxiliary agents, and can form the protective coating on a substrate after being used for the polyurethane glass fiber composite material.
The technical scheme adopted for solving the technical problems is as follows:
the ultraviolet light curing coating for the polyurethane glass fiber composite material comprises the following components in parts by weight:
the UV resin is prepared from phenolic epoxy acrylate oligomer and polyurethane acrylate oligomer according to the mass ratio of (4-5): 1.
Optionally, the epoxy group-containing phenolic epoxy acrylate oligomer is prepared as follows: into a three-necked flask, 36.2g of a dioxane solution of 70% by mass of a novolac epoxy resin, 2.47g of a dioxane solution of 2% by mass of hydroquinone, 0.35g of a tetrabutylammonium bromide catalyst, 5.76g of acrylic acid were added, and the temperature was raised to 95 ℃ to react until the acid value was 0, and the reaction was stopped, thereby obtaining an epoxy group-containing novolac epoxy acrylate oligomer.
Optionally, the urethane acrylate oligomer is an aliphatic urethane acrylate oligomer.
Optionally, the UV monomer is a monofunctional monomer and a polyfunctional monomer according to the mass ratio (8-10): (5-9) a mixture.
Alternatively, the Shan Guan monomer is a cyclotrimethylol propane methylacrylate and the polyfunctional monomer is tris (2-hydroxyethyl) isocyanurate triacrylate.
Optionally, the adhesion promoter is a polyalkenyl phosphate compound.
Optionally, the anti-settling agent is fumed silica.
Optionally, the defoamer is a silicone-free foam breaking polymer solution.
Optionally, the filler is 1250-mesh talcum powder; the wax powder is polytetrafluoroethylene wax.
Optionally, the initiator is a free radical photoinitiator and a cationic photoinitiator according to a mass ratio of 5: 1.
The beneficial effects of the invention are as follows:
the ultraviolet light curing coating for the polyurethane glass fiber composite material provided by the invention takes the phenolic epoxy acrylate oligomer containing epoxy groups and the polyurethane acrylate oligomer as main resin, and combines monomers and other auxiliary agents, so that after the system is coated on the polyurethane glass fiber composite material, the ultraviolet light curing coating is cured by a UV high-pressure mercury lamp, and a protective coating can be rapidly formed, so that the physical injury to a processing worker in the processing process of the polyurethane glass fiber composite material is reduced; the coating has good protection, reduces the pollution of the polyurethane glass fiber composite material to the environment in transportation, and reduces the damage and waste caused by the transportation; the coating has good cold and hot temperature difference resistance, temperature resistance and corrosion resistance, is beneficial to improving the processing performance of the polyurethane glass fiber composite material on the basis of not affecting the physical performance of the polyurethane glass fiber composite material, and prolongs the service life of the polyurethane glass fiber composite material.
Detailed Description
The present invention will now be described in further detail. The embodiments described below are exemplary and intended to illustrate the invention and should not be construed as limiting the invention, as all other embodiments, based on which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of the invention.
In order to solve the problem of poor high temperature resistance of a protective coating of a polyurethane glass fiber composite material in the prior art, the invention provides an ultraviolet light curing coating for the polyurethane glass fiber composite material, which comprises the following components in parts by weight:
wherein the UV resin is phenolic epoxy acrylate oligomer containing epoxy groups and polyurethane acrylate oligomer according to the mass ratio of (4-5): 1.
The existing polyurethane glass fiber composite material is usually used as a protective coating layer by using a coating prepared from a solvent coating, and the solvent coating is not only unfavorable for environmental protection, but also has low drying speed and poor cold and heat temperature difference resistance; in the use, especially when being used for door and window section bar, because indoor outer difference in temperature to and the change of early, middle and late temperature, the protective coating who is used for its surface is required to have excellent cold and hot temperature difference performance, otherwise easily appears the film bubble phenomenon in the use, leads to damage such as film breakage for glass fiber exposes, can not only influence its life, still easily causes the injury to the human body, exists great potential safety hazard.
The ultraviolet light curing coating for the polyurethane glass fiber composite material provided by the invention takes the phenolic epoxy acrylate oligomer containing epoxy groups and the polyurethane acrylate oligomer as main resin, and combines monomers and other auxiliary agents, so that after the system is coated on the polyurethane glass fiber composite material, the ultraviolet light curing coating is cured by a UV high-pressure mercury lamp, and a protective coating can be rapidly formed, so that the physical injury to a processing worker in the processing process of the polyurethane glass fiber composite material is reduced; the coating has good protection, reduces the pollution of the polyurethane glass fiber composite material to the environment in transportation, and reduces the damage and waste caused by the transportation; the coating has good cold and hot temperature difference resistance, temperature resistance and corrosion resistance, is beneficial to improving the processing performance of the polyurethane glass fiber composite material on the basis of not affecting the physical performance of the polyurethane glass fiber composite material, and prolongs the service life of the polyurethane glass fiber composite material.
Specifically, the epoxy group-containing phenolic epoxy acrylate oligomer is preferably prepared according to the following method:
into a three-necked flask, 36.2g of a dioxane solution of 70% by mass of a novolac epoxy resin (containing 0.1mol of epoxy groups), 2.47g of a dioxane solution of 2% by mass of hydroquinone, 0.35g of tetrabutylammonium bromide catalyst, 5.76g of acrylic acid (0.08 mol) were charged, and the reaction was stopped after heating to 95℃until the acid value was 0, to obtain an epoxy group-containing novolac epoxy acrylate oligomer.
In the preparation process of the epoxy group-containing phenolic epoxy acrylate oligomer, dioxane is used as a solvent, so that the conversion rate of resin is improved, and the adhesive force, the cold and heat temperature difference resistance and the high temperature resistance of the coating are improved.
In order to further improve the high temperature resistance and the cold and hot temperature difference resistance of the coating, the epoxy equivalent (g/eq) of the phenolic epoxy resin is preferably 170-190, preferably the phenolic epoxy resin is F-48 or F-44, and further preferably F-48.
In addition, the phenolic aldehyde epoxy acrylate oligomer prepared by the method is an epoxy group-containing phenolic aldehyde acrylate oligomer, and the epoxy group-containing phenolic aldehyde acrylate oligomer is multifunctional acrylate and has free radical and cation dual-curing performance, so that the phenolic aldehyde acrylate oligomer can be subjected to free radical polymerization curing, and then can be subjected to cation curing, and has higher conversion rate, high reactivity and high crosslinking density; the benzene ring has high density, high rigidity and high esterification degree; the preparation process combines the components and the process conditions, so that the prepared phenolic acrylate oligomer is beneficial to improving the heat resistance, the cold and heat temperature difference resistance, the chemical resistance, the surface hardness and the adhesive force of the system after being introduced into the system.
The polyurethane acrylate oligomer is preferably aliphatic polyurethane acrylate oligomer, and is further preferably ETERCURE 6157B-80 aliphatic polyurethane acrylate of Changxing special material (pearl sea) limited company, and the aliphatic polyurethane acrylate oligomer is beneficial to improving the water resistance, heat resistance, weather resistance and toughness of the system.
According to the invention, through the compounding of the epoxy-containing phenolic epoxy acrylate oligomer and the polyurethane acrylate oligomer, the coating prepared by the ultraviolet light-cured coating can be cured rapidly, and the coating has the cold and hot temperature difference resistance, high temperature resistance and physical properties, and meets the use requirements of polyurethane glass fiber composite materials.
In order to give consideration to the curing speed and physical properties of the coating, the UV monomer is preferably a monofunctional monomer and a polyfunctional monomer according to the mass ratio (8-10): (5-9) a mixture.
Further preferred monofunctional monomers are CTFA cyclotrimethylolpropane methylacrylate, and particularly preferred are changxing specialty materials (pearlsea) EM212, inc; the monomer has the advantages of ring structure, very good flexibility, low viscosity, low shrinkage, low odor, good chemical resistance, high double bond conversion rate, high curing speed and the like, and mainly has the advantages of reducing the viscosity, improving the surface wear resistance, resisting water and weather, reducing the shrinkage rate of the coating and the like in the system.
The preferred multifunctional monomer is a trifunctional monomer, and further preferred is THEICTA tri (2-hydroxyethyl) isocyanurate triacrylate, particularly preferred is Changxing Special materials (Zhuhai) Co., ltd. EM2308; the monomer has good low volume shrinkage, excellent water resistance and chemical resistance, excellent hardness and wear resistance and good impact resistance, and is mainly used for improving the reaction speed of the coating and providing excellent physical and chemical properties.
The adhesion promoter is preferably a polyalkenyl acrylic acid phosphate compound, and is further preferably AH-100L of Fang Ming chemical industry limited in Xingyi, wherein AH-100L can participate in instant initiation polymerization together with the UV main resin, special terminal ester groups in the auxiliary agent are introduced into the cured coating, the boiling resistance, acid and alkali resistance and chemical corrosion resistance of the UV coating are improved, and the AH-100L has good storage stability when being added into the UV coating.
The preferred anti-settling agent of the present invention is fumed silica, and particularly preferably fumed silica M-5 of the Kabot company.
The preferred defoamer of the present invention is a silicone-free foam breaking polymer solution, and is particularly preferred to be DEGO Airex920.
The filler is preferably 1250-mesh talcum powder, has soft texture, lubricity, fire resistance, insulativity, acid and alkali resistance, is inactive in chemical property, is insoluble in water, has filling property and can reduce cost.
The wax powder is preferably polytetrafluoroethylene wax, and the polytetrafluoroethylene wax has excellent heat resistance, weather resistance, cold resistance, low friction, non-tackiness, chemical stability, electrical insulation property and other excellent properties, and has small average particle size, so that the polytetrafluoroethylene wax has good dispersibility and is easy to blend with other materials uniformly; polytetrafluoroethylene wax is a white low molecular weight free flowing powder, due to the presence of- (-CF) 2 -CF 2 -) n The coating has a stable molecular structure, excellent chemical resistance, thermal stability, high weather resistance and ageing resistance (more than ten years), ultraviolet resistance, high temperature resistance (the long-term application temperature is about 260 ℃), wide use temperature range (-200 to +260 ℃), good non-tackiness, high electrical insulation (1017 ohm cm) and high flame retardance, thereby being beneficial to improving the weather resistance, the wear resistance, the temperature resistance, the cold resistance and the like of the coating; the invention is preferably a Ceridust 9610F polytetrafluoroethylene modified wax from Clariant, germany.
In order to ensure dual curing, the initiator is preferably a free radical photoinitiator and a cationic photoinitiator according to the mass ratio of 5:1, and particularly preferably the free radical photoinitiator is a mixture of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide TPO and 1-hydroxy-cyclohexyl-phenyl ketone 184 in a mass ratio of 1:4; preferably the cationic photoinitiator is Omnirad 250.
The coating obtained by the invention is subjected to UV curing on the polyurethane glass fiber composite material (GRPU) in a roller coating mode, so that the ultraviolet light curing coating of the polyurethane glass fiber composite material forms a protective coating on the substrate, the problem brought by the polyurethane glass fiber composite material (GRPU) in the deep processing process can be effectively solved, the protection of the polyurethane glass fiber composite material (GRPU) in the transportation process is facilitated, the utilization rate and the processing performance of the polyurethane glass fiber composite material (GRPU) are greatly improved, and the application and popularization of the polyurethane glass fiber composite material (GRPU) are facilitated.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
The phenolic epoxy acrylate oligomers in the examples and comparative examples of the present invention were prepared as follows, without any particular explanation:
into a three-necked flask, 36.2g of a dioxane solution (containing 0.1mol of epoxy group) of 70% by mass of a novolac epoxy resin (F-48), 2.47g of a dioxane solution of 2% by mass of hydroquinone, 0.35g of tetrabutylammonium bromide catalyst, 5.76g of acrylic acid (0.08 mol) were charged, and the reaction was stopped by heating to 95℃until the acid value was 0, to obtain an epoxy group-containing novolac epoxy acrylate oligomer (a radical and cationic dual-cure UV oligomer), which was designated as self-made oligomer I.
Example 1
The embodiment provides an ultraviolet light curing coating for polyurethane glass fiber composite materials, which comprises the following components in parts by weight:
example 2
The embodiment provides an ultraviolet light curing coating for polyurethane glass fiber composite materials, which comprises the following components in parts by weight:
example 3
The embodiment provides an ultraviolet light curing coating for polyurethane glass fiber composite materials, which comprises the following components in parts by weight:
example 4
The embodiment provides an ultraviolet light curing coating for polyurethane glass fiber composite materials, which comprises the following components in parts by weight:
example 5
The embodiment provides an ultraviolet light curing coating for polyurethane glass fiber composite materials, which comprises the following components in parts by weight:
example 6
The embodiment provides an ultraviolet light curing coating for polyurethane glass fiber composite materials, which comprises the following components in parts by weight:
comparative example 1
The difference between this comparative example and example 1 is that the homemade oligomer I was replaced with the phenolic epoxy acrylate AgiSyn 9760 from Kaiyi chemical Co., ltd.
Comparative example 2
This comparative example differs from example 1 in that homemade oligomer I was replaced with the Shanghai Zhan New company epoxy acrylate EBECRYL 1710.
Comparative example 3
The difference between this comparative example and example 1 is that homemade oligomer II was used instead of homemade oligomer I, wherein homemade oligomer II was prepared as follows:
36.2g of dioxane solution (containing 0.1mol of epoxy group) of 70% phenolic epoxy resin (F-48) in mass fraction, 2.47g of dioxane solution of 2% hydroquinone in mass fraction, 0.35g of tetrabutylammonium bromide catalyst, heating to 90 ℃, stirring uniformly, dropwise adding acrylic acid (molar ratio of carboxyl to epoxy group=1:1) and 0.35g of tetrabutylammonium bromide catalyst, and maintaining the reaction temperature at 110 ℃ for reacting for 4H until the acid value is less than or equal to 5KOH/g, thus obtaining the self-made oligomer II.
Comparative example 4
The difference between this comparative example and example 1 is that homemade oligomer III was used instead of homemade oligomer I, wherein homemade oligomer III was prepared as follows:
25.3g of phenolic epoxy resin (F-51) and (0.05) g of hydroquinone are added into a three-neck flask, the temperature is raised to 90 ℃, the mixture is stirred uniformly, acrylic acid (molar ratio of carboxyl to epoxy group=0.8:1) and 0.35g of tetrabutylammonium bromide catalyst are added dropwise, the reaction temperature is maintained at 95 ℃, the reaction is carried out until the acid value is 0, and the self-made oligomer III is obtained.
Comparative example 5
The comparative example provides an ultraviolet light curing coating for polyurethane glass fiber composite materials, which comprises the following components in parts by weight:
comparative example 6
The comparative example provides an ultraviolet light curing coating for polyurethane glass fiber composite materials, which comprises the following components in parts by weight:
comparative example 7
This comparative example differs from example 1 in that the Changxing Special materials (Zhuhai) Limited, ETERCURE 6157B-80, were replaced with Changxing Special materials (Zhuhai) Limited, multifunctional urethane acrylate ETERCURE 6145-100.
Comparative example 8
This comparative example differs from example 1 in that the Change Special materials (Zhuhai) Co., ltd. ETERCURE 6157B-80 was replaced with an aliphatic urethane acrylate.
Comparative example 9
The difference between this comparative example and example 1 is that EM212 was replaced with an aliphatic urethane acrylate of EM214 of the long-felt special material (zhuhai) limited.
Comparative example 10
The difference between this comparative example and example 1 is that EM2308 was replaced with an aliphatic urethane acrylate of EM231 of the long-life special material (zhuhai) limited.
Comparative example 11
The difference between this comparative example and example 1 is that AH-100L was replaced with methacrylic acid modified phosphate EM39 from Changxing specialty materials (Zhuhai Co., ltd.).
Comparative example 12
The difference between this comparative example and example 1 is that 1250 mesh transparent powder was used instead of 1250 mesh talc powder.
Application of
According to the formula amount, the components of the embodiment and the comparative example are uniformly mixed to obtain the ultraviolet light-cured coating applied to the polyurethane glass fiber composite material, and the ultraviolet light-cured coating obtained in the embodiment and the comparative example is coated on the polyurethane glass fiber composite material (GRPU) by a roller coating mode to 80g/cm 2 After UV curing, the ultraviolet light curing coating of the polyurethane glass fiber composite material forms a protective coating on the substrate, and then the following performance test is carried out:
1. adhesion test: the test was performed according to the standard GB/T4893.4-2013 adhesion cross cut assay.
2. High and low temperature cycle test for seven days: according to the standard GB4893.7-2013 furniture surface paint film cold and heat resistance temperature difference measuring method.
3. Scratch resistance test method reference: EN 16094 laminate floor covering test method for micro scratch resistance.
4. Hardness testing: the test was carried out according to the pencil test of the hardness of the coating film of standard GB 6739-86.
5. Placing in a high temperature oven at 100 ℃ for seven days, and testing whether cracking occurs.
The test results are shown in Table 1:
TABLE 1
From the data in table 1, it is shown that the coating prepared from the ultraviolet light curing coating provided by each embodiment of the invention has excellent adhesion with the polyurethane glass fiber composite material, and also has good cold and hot temperature difference resistance, temperature resistance, scratch resistance and surface hardness, and on the basis of not affecting the physical properties of the polyurethane glass fiber composite material, the processing performance of the polyurethane glass fiber composite material is improved, the application range of the coating is enlarged, and the service life of the coating is prolonged.
Comparative examples 1-2 the coating adhesion was reduced and the cold and hot temperature difference resistance and high temperature resistance of the paint film prepared in comparative example 2 were reduced compared with example 1 by replacing the self-made oligomer I with the commercially available conventional phenolic epoxy acrylate oligomer, respectively.
In the preparation of the self-made oligomer II in comparative example 3, the molar ratio of carboxyl to epoxy groups is changed to 1:1, the prepared coating has large curing shrinkage, obvious influence on adhesive force and poor cold and heat temperature difference resistance.
Comparative example 4 an oligomer was prepared according to a conventional preparation method, and in the preparation process using this method, if the novolac epoxy resin was F-48 or F-44, the system was too viscous, so that it was difficult to mix the novolac epoxy resin with stirring, and the reaction process was difficult to control, and the test could not be continued; after the phenolic epoxy resin is replaced by F-51, the reaction can be continued, but the problem of difficult control of the reaction process still exists; the coating prepared by the comparative example has low curing rate, reduces production efficiency, increases curing time, and influences adhesive force and water resistance of the coating.
Comparative example 5 reduced the amount of self-made oligomer I added, and the temperature resistance of the prepared coating was poor and the protective effect was poor, as compared with example 1.
Comparative example 6, compared with example 1, increased the amount of self-made oligomer I added, and the prepared coating had a larger shrinkage, which was not conducive to control of adhesion.
In the comparative example 7 and the comparative example 8, different polyurethane acrylic acid ester is selected to replace 6157B-80 respectively, the cold and hot temperature difference resistance and the high temperature resistance of a paint film are reduced, and meanwhile, the adhesive force of a coating in the comparative example 7 is obviously reduced.
Comparative example 9 and comparative example 10 the monofunctional monomer and the polyfunctional monomer of example 1 were replaced, respectively, wherein the coating of comparative example 9 had significantly reduced resistance to heat and cold cycles and the coating of comparative example 10 had reduced adhesion.
Comparative example 11 and comparative example 12 each had only the adhesion promoter and filler in the system replaced, but both had poor heat and cold cycle resistance of the coating.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (10)
1. An ultraviolet light curing coating for polyurethane glass fiber composite material is characterized in that,
the coating comprises the following components in parts by weight:
the UV resin is prepared from phenolic epoxy acrylate oligomer containing epoxy groups and polyurethane acrylate oligomer according to the mass ratio of (4-5): 1.
2. The ultraviolet light-curable coating for polyurethane glass fiber composite material according to claim 1, wherein the epoxy group-containing novolac epoxy acrylate oligomer is prepared by the following method: 36.2g of dioxane solution of 70% of phenolic epoxy resin in mass fraction, 2.47g of dioxane solution of 2% of hydroquinone in mass fraction, 0.35g of tetrabutylammonium bromide catalyst and 5.76g of acrylic acid are added into a three-neck flask, and the temperature is raised to 95 ℃ to react until the acid value is 0, and the reaction is stopped, so that the phenolic epoxy acrylate oligomer containing epoxy groups is obtained.
3. The ultraviolet light-curable coating for polyurethane glass fiber composite according to claim 2, wherein the urethane acrylate oligomer is an aliphatic urethane acrylate oligomer.
4. The ultraviolet light-curable coating for polyurethane glass fiber composite material according to claim 2, wherein the UV monomer is a monofunctional monomer and a polyfunctional monomer in a mass ratio of (8-10): (5-9) a mixture.
5. The ultraviolet light-curable coating for polyurethane glass fiber composite according to claim 4, wherein the Shan Guan monomer is cyclotrimethylol propane methylacrylate and the polyfunctional monomer is tris (2-hydroxyethyl) isocyanurate triacrylate.
6. The ultraviolet light-curable coating for polyurethane glass fiber composite material according to any one of claims 1 to 5, wherein the adhesion promoter is a polyalkenyl acrylic phosphate compound.
7. The ultraviolet light-curable coating for polyurethane glass fiber composite material according to any one of claims 1 to 5, wherein the anti-settling agent is fumed silica.
8. The ultraviolet light-curable coating for polyurethane glass fiber composite material according to any one of claims 1 to 5, wherein the antifoaming agent is a silicone-free foam breaking polymer solution.
9. The ultraviolet light-curable coating for polyurethane glass fiber composite material according to any one of claims 1 to 5, wherein the filler is 1250 mesh talc; the wax powder is polytetrafluoroethylene wax.
10. The ultraviolet light-curable coating for polyurethane glass fiber composite material according to any one of claims 1 to 5, wherein the initiator is a radical photoinitiator and a cationic photoinitiator in a mass ratio of 5: 1.
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