CN106632741B - Compound net taste photoinitiator and ultraviolet-curing paint - Google Patents
Compound net taste photoinitiator and ultraviolet-curing paint Download PDFInfo
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- CN106632741B CN106632741B CN201611092888.1A CN201611092888A CN106632741B CN 106632741 B CN106632741 B CN 106632741B CN 201611092888 A CN201611092888 A CN 201611092888A CN 106632741 B CN106632741 B CN 106632741B
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- photoinitiator
- net taste
- acrylate
- hydroxyl
- ultraviolet
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- 239000003973 paint Substances 0.000 title claims abstract description 72
- 150000001875 compounds Chemical class 0.000 title claims abstract description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011787 zinc oxide Substances 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 239000012948 isocyanate Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 23
- 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 20
- 229920000728 polyester Polymers 0.000 claims description 20
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 20
- 239000003085 diluting agent Substances 0.000 claims description 17
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 12
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical class C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- -1 hydroxyl ethyl Chemical group 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 32
- 238000000576 coating method Methods 0.000 abstract description 32
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 239000005416 organic matter Substances 0.000 abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006303 photolysis reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 41
- 238000000016 photochemical curing Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 8
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000002525 ultrasonication Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000002023 wood Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000035943 smell Effects 0.000 description 5
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- VUZHZDBMVSHDRE-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OCCCOC(=O)C=C VUZHZDBMVSHDRE-UHFFFAOYSA-N 0.000 description 1
- PYGXUPRQBBNETH-UHFFFAOYSA-N acetic acid;2-hydroxypropyl prop-2-enoate Chemical compound CC(O)=O.CC(O)COC(=O)C=C PYGXUPRQBBNETH-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/284—Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
Abstract
The present invention relates to a kind of compound net taste photoinitiators and ultraviolet-curing paint.The net taste photoinitiator is included following weight percentage components：Zinc oxide 30~70%, macromolecular photoinitiator 30~70%, wherein, the macromolecular photoinitiator is prepared by the acrylic acid of the photoinitiator of hydroxyl, isocyanates and hydroxyl.The net taste photoinitiator can effectively overcome the odor problem that the volatility organic molecule discharged after organic photoinitiator photodissociation generates, and efficiency of initiation is high, ultraviolet-curing paint conversion ratio can be improved, thus smell and volatile organic matter that unreacting material in remaining coating is discharged are further reduced, make the net taste of the paint film after photopolymerization and is had excellent performance.
Description
Technical field
The present invention relates to photoinitiator, more particularly to compound net taste photoinitiator and ultraviolet-curing paint.
Background technology
Ultraviolet-curing paint is practically free of volatile organic solvent, with energy consumption is low, reaction speed is fast, wiper ring
The advantages that guarantor.The formula system of one ultraviolet-curing paint includes at least following three components：1. photosensitive resin (or pre-polymerization
Object, oligomer), be the most basic physical and chemical performance of coating and paint film source, determine the curing of entire formula system
The performance of rate and material；2. reactive diluent is mainly used for the viscosity of adjusting coating formula system；3. photoinitiator, in purple
Under the irradiation of outer light, the active group (free radical or cation) that photopolymerization occurs for above two substance can be caused by generating.
Net taste coating technology is one of developing direction of current ultraviolet-curing paint.
According to light-initiated mechanism, photoinitiator can be divided into free radical photo-initiation and cation light initiator.By freedom
Base initiator generates the mechanism of living radical, and free radical photo-initiation can be divided into hydrogen-capture-type light initiator and draw with cracking type light
Send out agent.In ultraviolet-curing paint, it is most widely used with free radical photo-initiation.Although the light in entire formula system
The dosage of initiator is not high, and common mass content is between 1-10%, and still, photoinitiator is the pass of ultraviolet-curing paint
One of key component part.Ideal photoinitiator has following four feature：1. higher light-initiated efficiency；2. higher delustring system
Number；3. preferable bin stability；4. the preferable feature of environmental protection：Photoinitiator and its photodestruciton product should low toxicity, low smells.
According to the chemical composition of molecule, photoinitiator can be divided into organic photoinitiator, inorganic photoinitiator, macromolecular light and draw
Send out agent etc..What photoinitiator was usually used at present is organic photoinitiator, such as 2- hydroxy-2-methyl -1- phenyl -1- acetone
(1173 photoinitiator), 1- hydroxycyclohexyl phenyl ketones (184 photoinitiator) and 2,4,6- trimethylbenzoyls-hexichol
Base phosphine oxide (TPO photoinitiator) etc..After ultraviolet light photolysis occurs for these organic photoinitiators, generates work
Property group (free radical or cation), a part of photolytic product participates in causing photopolymerization reaction, the production of another part photolytic product
It gives birth to and releases benzene, the small molecules such as aldehyde, ketone, certain harm is all generated to environment and personnel's health.It is and inorganic light-initiated
Agent or macromolecular photoinitiator are expensive since the more organic photoinitiator of light-initiated efficiency is slightly lower, therefore using less.
Up to the present net taste coating technology is one of developing direction of ultraviolet-curing paint, but, photoinitiator is to purple
The net taste influential effect of outer photocureable coating has not been reported.
Invention content
Based on this, it is necessary to which organic molecule will not be generated, and efficiency of initiation is high, can improve UV light by providing one kind
Change the compound net taste photoinitiator of coating conversion ratio.
A kind of compound net taste photoinitiator, including following weight percentage components：
Zinc oxide 30~70%
Macromolecular photoinitiator 30~70%,
Wherein, the macromolecular photoinitiator by the photoinitiator of hydroxyl, isocyanates and hydroxyl acrylic acid system
It is standby to form.
Include in one of the embodiments, following weight percentage components：
Zinc oxide 45~55%
Macromolecular photoinitiator 45~55%.
The zinc oxide is nano zine oxide in one of the embodiments, and grain size is 10~200nm.
The preparation method of above-mentioned nano zine oxide is preferably：By zinc oxide in 50~70 DEG C of vacuum drying chamber temperature ,-
Dry 2~4 hours under the conditions of the relative vacuum pressures of 0.09~-0.1MPa, then with ultrasonication 10~60 minutes, obtain
Nano zine oxide average diameter for 10-200 rans, purity is more than 99%.
The grain size of the zinc oxide is 20~130nm in one of the embodiments,.
The macromolecular photoinitiator is 1.05~1.1 by molar ratio in one of the embodiments,:1:1 hydroxyl
Photoinitiator, isocyanates and hydroxyl acrylic acid be prepared.
The preparation method of the macromolecular photoinitiator includes the following steps in one of the embodiments,：
The isocyanates with the acrylic acid of hydroxyl is mixed, is reacted 2~4 hours at 30~50 DEG C；Add institute
The photoinitiator of hydroxyl is stated, is reacted 2~4 hours at 60~80 DEG C.
In one of the embodiments, the photoinitiator of the hydroxyl for 2- hydroxy-2-methyl -1- phenyl -1- acetone,
One kind in 1- hydroxycyclohexyl phenyl ketones, 2- hydroxyls -4'- (2- hydroxy ethoxies) -2- methyl phenyl ketones；The isocyanates
For isophorone diisocyanate；The acrylic acid of the hydroxyl is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, acrylic acid
One kind in hydroxypropyl acrylate, hydroxy propyl methacrylate.
The present invention also provides a kind of ultraviolet-curing paint, using the net taste photoinitiator as photoinitiator.
Include the following raw material component in one of the embodiments,：
The present invention also provides the preparation methods of the compound ultraviolet-curing paint, include the following steps：
By the epoxy acrylate, urethane acrylate, polyester acrylate and reactive diluent respectively 50~
80 DEG C, vacuum pressure is pre-processes 3~6 hours under conditions of -0.095MPa；
The pretreated epoxy acrylate, urethane acrylate, polyester acrylate and activity is mixed to dilute
Agent and the net taste photoinitiator, you can.
Compared with prior art, the invention has the advantages that：
The compound net taste photoinitiator of the present invention, is compounded using zinc oxide and specific macromole evocating agent.
Wherein, zinc oxide will not generate odorous product after photodissociation, coordinate specific macromolecular as a kind of inorganic photoinitiator
Photoinitiator enhances the light-initiated efficiency of zinc oxide, forms the net taste photoinitiator of inorganic/organic composite type, can effectively overcome
Odor problem that the volatility organic molecule discharged after organic photoinitiator photodissociation generates, and the net taste photoinitiator draws
It sends out efficient, ultraviolet-curing paint conversion ratio can be improved, be thus further reduced unreacting material institute in remaining coating
The smell and volatile organic matter of release make the net taste of the paint film after photopolymerization and have excellent performance.
The ultraviolet-curing paint of the present invention, using zinc oxide and specific macromole evocating agent compounding as photocatalysis
Agent, gained paint film property is excellent after photopolymerization and net taste.Further use epoxy acrylate, urethane acrylate and polyester
Acrylate cooperation can optimize the solidification rate of entire formula system and the performance of material, average double bond as photosensitive resin
Conversion ratio and gel fraction are all higher than 95%, and paint film is transparent or translucent, and thickness is 20 μm~100 μm.
The preparation method of the ultraviolet-curing paint of the present invention, first under proper temperature and vacuum condition, to photosensitive tree
Fat and reactive diluent are pre-processed, and then the method for removing volatile organic matter is mixed again, be further reduced formula
Substance with smell in system reduces the smell of photocureable coating.
Description of the drawings
Fig. 1 is the infrared spectrogram of compound net taste photoinitiator that embodiment 1 is prepared；
The double bond conversion rate of ultraviolet-curing paint and photopolymerization rate of polymerization is prepared for embodiment 1 in Fig. 2, wherein,
The conversion ratio of double bond is shown in " ▲ ", and the photopolymerization rate of double bond is shown in " ■ ", double when cure times are 6 seconds
Key conversion ratio is about 95%.
Specific embodiment
The compound net taste photoinitiator and ultraviolet-curing paint of the present invention are made below in conjunction with specific embodiment
Further details of explanation.
Involved primary raw material source is as follows in the embodiment of the present invention：
Nano zine oxide：South China Science ＆ Engineering University's laboratory self-control, average diameter are 10~200 rans；
Isophorone diisocyanate：Wanhua Chemical Group Co., Ltd., technical grade；
The photoinitiator of hydroxyl：2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxycyclohexyl phenyl ketones, 2-
Hydroxyl -4'- (2- hydroxy ethoxies) -2- methyl phenyl ketones etc., German BASF Co., Ltd, technical grade；
The acrylic acid of hydroxyl：Hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and methacrylic acid
Hydroxypropyl acrylate etc., Mitsubishi chemical company, technical grade；
Photosensitive resin and reactive diluent：Epoxy acrylate, urethane acrylate, polyester acrylate and activity are dilute
Release agent (1,6- hexylene glycol double methacrylate, tripropylene glycol double methacrylate), Sartomer (Guangzhou) Chemical Co., Ltd., industry
Grade.
The involved surface treatment method to woodenware is as follows in embodiment：
First the impurity such as dust, the greasy dirt on woodenware surface are removed totally, with sand paper polishing woodenware surface, remove polishing
After impurity, unsaturated polyester type putty is scraped into place into gap and out-of-flatness with scraper plate, after putty parches, is ground with sand paper
Light cleans the impurity of polishing with staple.
Embodiment 1
The present embodiment uses a kind of compound net taste photoinitiator, including following weight percentage components：
Nano zine oxide 30%
Macromolecular photoinitiator 70%.
The preparation method of above-mentioned nano zine oxide：By zinc oxide in vacuum drying chamber temperature 60 C, about -0.095MPa's
Dry 3 hours under the conditions of relative vacuum pressures, then with ultrasonication 10 minutes, the average diameter for obtaining nano zine oxide is
127 nanometers, purity is more than 99%；
The synthesis of macromolecular photoinitiator：Weigh 2- hydroxy-2-methyl -1- phenyl -1- acetone, isophorone diisocyanate
Ester and hydroxy-ethyl acrylate, molar ratio 1.05:1:1；By isophorone diisocyanate and hydroxy-ethyl acrylate first 50
It is reacted 2 hours at DEG C, 2- hydroxy-2-methyl -1- phenyl -1- acetone and 1- hydroxycyclohexyl phenyl ketones is added, at 60 DEG C
Lower reaction 4 hours；
The preparation of net taste photoinitiator：Above-mentioned nano zine oxide is added in macromolecular photoinitiator in batches, in room temperature
Under stir evenly, you can, infrared spectrogram is as shown in Figure 1.
Using the ultraviolet-curing paint of above-mentioned net taste photoinitiator, preparation method includes the following steps：
(1) vacuum removal volatile organic matter：Choose epoxy acrylate, urethane acrylate, polyester acrylate
And reactive diluent (1,6- hexylene glycol double methacrylate), respectively at 50 DEG C, vacuum pressure takes off under conditions of being -0.095MPa
Except volatile organic matter 6 hours；
(2) production of ultraviolet-curing paint：Be gradually added into batches weight percent 4% above-mentioned net taste photoinitiator,
40% epoxy acrylate, 30% urethane acrylate, 16% polyester acrylate and 10% reactive diluent, at normal temperatures
It stirs evenly, you can.
The photocuring of coating：With UV curtain coaters on wood furniture surface the above-mentioned ultraviolet-curing paint of showering, wet coating thickness
About 30 μm~55 μm of degree, on the photo solidification machine of 2~5kw, with 0.1~1 m/min of speed, adjustment photocureable energy is about
80~400mJ/cm2, the coast of paint film of 25 μm~50 μm of UV light chemical conversion.Test the cured paint film of ultraviolet light photocuring it
It is net taste afterwards, average conversion is 95% (as shown in Figure 2), and average gel rate (crosslinking ratio) is 97%, and film thickness is
25 μm~50 μm, paint film property is above standard in " ultraviolet light (UV) solidified carpentry coating HG/T 3655-2012 " and finishing coat is wanted
It asks.
Embodiment 2
The present embodiment uses a kind of compound net taste photoinitiator, including following weight percentage components：
Nano zine oxide 40%
Macromolecular photoinitiator 60%.
The preparation method of above-mentioned nano zine oxide：By zinc oxide in vacuum drying chamber temperature 60 C, about -0.095MPa's
Dry 3 hours under the conditions of relative vacuum pressures, then with ultrasonication 20 minutes, the average diameter for obtaining nano zine oxide is
108 nanometers, purity is more than 99%；
The synthesis of macromolecular photoinitiator：Weigh 1- hydroxycyclohexyl phenyl ketones, isophorone diisocyanate and first
Base hydroxy-ethyl acrylate, molar ratio 1.1:1:1；By isophorone diisocyanate and hydroxyethyl methacrylate first 30
It is reacted 4 hours at DEG C, adds 1- hydroxycyclohexyl phenyl ketones, reacted 3 hours at 70 DEG C；
The preparation of net taste photoinitiator：Above-mentioned nano zine oxide is added in macromolecular photoinitiator in batches, in room temperature
Under stir evenly, you can.
Using the ultraviolet-curing paint of above-mentioned net taste photoinitiator, preparation method includes the following steps：
(1) vacuum removal volatile organic matter：Choose epoxy acrylate, urethane acrylate, polyester acrylate
And reactive diluent (1,6- hexylene glycol double methacrylate), respectively at 60 DEG C, vacuum pressure takes off under conditions of being -0.095MPa
Except volatile organic matter 5 hours；
(2) production of ultraviolet-curing paint：Be gradually added into batches weight percent 5% above-mentioned net taste photoinitiator,
25% epoxy acrylate, 50% urethane acrylate, 15% polyester acrylate and 5% reactive diluent, at normal temperatures
It stirs evenly, you can.
The photocuring of coating：With UV curtain coaters on wood furniture surface the above-mentioned ultraviolet-curing paint of showering, wet coating thickness
About 30 μm~55 μm of degree, on the photo solidification machine of 2~5kw, with 0.1~1 m/min of speed, adjustment photocureable energy is about
80~400mJ/cm2, the coast of paint film of 25 μm~50 μm of UV light chemical conversion.Test the cured paint film of ultraviolet light photocuring it
It is net taste afterwards, average conversion 96%, average gel rate (crosslinking ratio) is 96%, and film thickness is 25 μm~50 μm,
Paint film property is above standard the requirement in " ultraviolet light (UV) solidified carpentry coating HG/T 3655-2012 " to finishing coat.
Embodiment 3
The present embodiment uses a kind of compound net taste photoinitiator, including following weight percentage components：
Nano zine oxide 30%
Macromolecular photoinitiator 70%.
The preparation method of above-mentioned nano zine oxide：By zinc oxide in vacuum drying chamber temperature 60 C, about -0.095MPa's
Dry 3 hours under the conditions of relative vacuum pressures, then with ultrasonication 30 minutes, the average diameter for obtaining nano zine oxide is
82 nanometers, purity is more than 99%；
The synthesis of macromolecular photoinitiator：Weigh 2- hydroxyls -4'- (2- hydroxy ethoxies) -2- methyl phenyl ketones, isophorone
Diisocyanate and hydroxypropyl acrylate, molar ratio 1.05:1:1；By isophorone diisocyanate and acrylic acid hydroxypropyl
Ester first reacts 2 hours at 50 DEG C, adds 2- hydroxyls -4'- (2- hydroxy ethoxies) -2- methyl phenyl ketones, reacts 3 at 80 DEG C
Hour；
The preparation of net taste photoinitiator：Above-mentioned nano zine oxide is added in macromolecular photoinitiator in batches, in room temperature
Under stir evenly, you can.
Using the ultraviolet-curing paint of above-mentioned net taste photoinitiator, preparation method includes the following steps：
(1) vacuum removal volatile organic matter：Choose epoxy acrylate, urethane acrylate, polyester acrylate
And reactive diluent (1,6- hexylene glycol double methacrylate), respectively at 70 DEG C, vacuum pressure takes off under conditions of being -0.095MPa
Except volatile organic matter 4 hours；
(2) production of ultraviolet-curing paint：Be gradually added into batches weight percent 6% above-mentioned net taste photoinitiator,
30% epoxy acrylate, 40% urethane acrylate, 15% polyester acrylate and 9% reactive diluent, at normal temperatures
It stirs evenly, you can.
The photocuring of coating：With UV curtain coaters on wood furniture surface the above-mentioned ultraviolet-curing paint of showering, wet coating thickness
About 30 μm~55 μm of degree, on the photo solidification machine of 2~5kw, with 0.1~1 m/min of speed, adjustment photocureable energy is about
80~400mJ/cm2, the coast of paint film of 25 μm~50 μm of UV light chemical conversion.Test the cured paint film of ultraviolet light photocuring it
It is net taste afterwards, average conversion 96%, average gel rate (crosslinking ratio) is 97%, and film thickness is 25 μm~50 μm,
Paint film property is above standard the requirement in " ultraviolet light (UV) solidified carpentry coating HG/T 3655-2012 " to finishing coat.
Embodiment 4
The present embodiment uses a kind of compound net taste photoinitiator, including following weight percentage components：
Nano zine oxide 60%
Macromolecular photoinitiator 40%.
The preparation method of above-mentioned nano zine oxide：By zinc oxide in vacuum drying chamber temperature 60 C, about -0.095MPa's
Dry 3 hours under the conditions of relative vacuum pressures, then with ultrasonication 40 minutes, the average diameter for obtaining nano zine oxide is
47 nanometers, purity is more than 99%；
The synthesis of macromolecular photoinitiator：Weigh 2- hydroxy-2-methyl -1- phenyl -1- acetone, isophorone diisocyanate
Ester and hydroxy propyl methacrylate, molar ratio 1.1:1:1；By isophorone diisocyanate and hydroxy propyl methacrylate
It is first reacted 3 hours at 40 DEG C, adds 2- hydroxy-2-methyl -1- phenyl -1- acetone, reacted 3 hours at 70 DEG C；
The preparation of net taste photoinitiator：Above-mentioned nano zine oxide is added in macromolecular photoinitiator in batches, in room temperature
Under stir evenly, you can.
Using the ultraviolet-curing paint of above-mentioned net taste photoinitiator, preparation method includes the following steps：
(1) vacuum removal volatile organic matter：Choose epoxy acrylate, urethane acrylate, polyester acrylate
And reactive diluent (tripropylene glycol double methacrylate), respectively at 80 DEG C, under conditions of vacuum pressure is -0.095MPa
Remove volatile organic matter 3 hours；
(2) production of ultraviolet-curing paint：Be gradually added into batches weight percent 3% above-mentioned net taste photoinitiator,
50% epoxy acrylate, 25% urethane acrylate, 15% polyester acrylate and 7% reactive diluent, at normal temperatures
It stirs evenly, you can.
The photocuring of coating：With UV curtain coaters on wood furniture surface the above-mentioned ultraviolet-curing paint of showering, wet coating thickness
About 30 μm~55 μm of degree, on the photo solidification machine of 2~5kw, with 0.1~1 m/min of speed, adjustment photocureable energy is about
80~400mJ/cm2, the coast of paint film of 25 μm~50 μm of UV light chemical conversion.Test the cured paint film of ultraviolet light photocuring it
It is net taste afterwards, average conversion 96%, average gel rate (crosslinking ratio) is 96%, and film thickness is 25 μm~50 μm,
Paint film property is above standard the requirement in " ultraviolet light (UV) solidified carpentry coating HG/T 3655-2012 " to finishing coat.
Embodiment 5
The present embodiment uses a kind of compound net taste photoinitiator, including following weight percentage components：
Nano zine oxide 70%
Macromolecular photoinitiator 30%.
The preparation method of above-mentioned nano zine oxide：By zinc oxide in vacuum drying chamber temperature 60 C, about -0.095MPa's
Dry 3 hours under the conditions of relative vacuum pressures, then with ultrasonication 60 minutes, the average diameter for obtaining nano zine oxide is
25 nanometers, purity is more than 99%；
The synthesis of macromolecular photoinitiator：Weigh 2- hydroxyls -4'- (2- hydroxy ethoxies) -2- methyl phenyl ketones, isophorone
Diisocyanate and hydroxy-ethyl acrylate, molar ratio 1.05:1:1；By isophorone diisocyanate and acrylic acid hydroxyl second
Ester first reacts 4 hours at 30 DEG C, adds 2- hydroxyls -4'- (2- hydroxy ethoxies) -2- methyl phenyl ketones, reacts 4 at 60 DEG C
Hour；
The preparation of net taste photoinitiator：Above-mentioned nano zine oxide is added in macromolecular photoinitiator in batches, in room temperature
Under stir evenly, you can.
Using the ultraviolet-curing paint of above-mentioned net taste photoinitiator, preparation method includes the following steps：
(1) vacuum removal volatile organic matter：Choose epoxy acrylate, urethane acrylate, polyester acrylate
And reactive diluent (tripropylene glycol double methacrylate), respectively at 60 DEG C, under conditions of vacuum pressure is -0.095MPa
Remove volatile organic matter 5 hours；
(2) production of ultraviolet-curing paint：Be gradually added into batches weight percent 5% above-mentioned net taste photoinitiator,
30% epoxy acrylate, 25% urethane acrylate, 30% polyester acrylate and 10% reactive diluent, at normal temperatures
It stirs evenly, you can.
The photocuring of coating：With UV curtain coaters on wood furniture surface the above-mentioned ultraviolet-curing paint of showering, wet coating thickness
About 30 μm~55 μm of degree, on the photo solidification machine of 2~5kw, with 0.1~1 m/min of speed, adjustment photocureable energy is about
80~400mJ/cm2, the coast of paint film of 25 μm~50 μm of UV light chemical conversion.Test the cured paint film of ultraviolet light photocuring it
It is net taste afterwards, average conversion 95%, average gel rate (crosslinking ratio) is 96%, and film thickness is 25 μm~50 μm,
Paint film property is above standard the requirement in " ultraviolet light (UV) solidified carpentry coating HG/T 3655-2012 " to finishing coat.
Comparative example 1
This comparative example be a kind of ultraviolet-curing paint, the same embodiment of process of the raw material used and UV photocurings
1-5, difference lies in：Do not include zinc oxide in its net taste photoinitiator used.Concrete technology is as follows.
A kind of photoinitiator of mixing of this comparative example, including following weight percentage components：
2- hydroxy-2-methyl -1- phenyl -1- acetone 30%
Macromolecular photoinitiator 70%.
The synthesis of macromolecular photoinitiator：Weigh 2- hydroxy-2-methyl -1- phenyl -1- acetone, isophorone diisocyanate
Ester and hydroxy-ethyl acrylate, molar ratio 1.05:1:1；By isophorone diisocyanate and hydroxy-ethyl acrylate first 50
It is reacted 2 hours at DEG C, 2- hydroxy-2-methyl -1- phenyl -1- acetone and 1- hydroxycyclohexyl phenyl ketones is added, at 60 DEG C
Lower reaction 4 hours；
Using the ultraviolet-curing paint of the photoinitiator of above-mentioned mixing, preparation method includes the following steps：
(1) vacuum removal volatile organic matter：Choose epoxy acrylate, urethane acrylate, polyester acrylate
And 1,6- hexylene glycol double methacrylate, respectively at 50 DEG C, removing volatility is organic under conditions of vacuum pressure is -0.095MPa
Object 6 hours；
(2) production of ultraviolet-curing paint：It is gradually added into the light-initiated of the above-mentioned mixing of weight percent 5% in batches
Agent, 40% epoxy acrylate, 30% urethane acrylate, 16% polyester acrylate and 10%1,6- hexylene glycol double third
Olefin(e) acid ester, stirs evenly at normal temperatures, you can.
The photocuring of coating：With UV curtain coaters on wood furniture surface the above-mentioned ultraviolet-curing paint of showering, wet coating thickness
About 30 μm~55 μm of degree, on the photo solidification machine of 2~5kw, with 0.1~1 m/min of speed, adjustment photocureable energy is about
80~400mJ/cm2, the coast of paint film of 25 μm~50 μm of UV light chemical conversion.Test the cured paint film of ultraviolet light photocuring it
To have certain smell afterwards, average conversion 92%, average gel rate (crosslinking ratio) is 90%, film thickness for 25 μm~
50 μm, paint film property is above standard the requirement in " ultraviolet light (UV) solidified carpentry coating HG/T 3655-2012 " to finishing coat.
Comparative example 2
This comparative example is a kind of ultraviolet-curing paint, the same embodiment of process of the raw material used and UV photocurings
1-5, difference lies in：Do not include the macromolecular photoinitiator in its net taste photoinitiator used.Concrete technology is as follows.
This comparative example uses a kind of photoinitiator of mixing, including following weight percentage components：
Nano zine oxide 30%
2- hydroxy-2-methyl -1- phenyl -1- acetone 70%.
The preparation method of above-mentioned nano zine oxide：By zinc oxide in vacuum drying chamber temperature 60 C, about -0.095MPa's
Dry 3 hours under the conditions of relative vacuum pressures, then with ultrasonication 10 minutes, the average diameter for obtaining nano zine oxide is
127 nanometers, purity is more than 99%；
The preparation of the photoinitiator of mixing：In batches by above-mentioned nano zine oxide be added to 2- hydroxy-2-methyl -1- phenyl -
In 1- acetone, stir evenly at normal temperatures, you can.
Using the ultraviolet-curing paint of the photoinitiator of above-mentioned mixing, preparation method includes the following steps：
(1) vacuum removal volatile organic matter：Choose epoxy acrylate, urethane acrylate, polyester acrylate
And reactive diluent (1,6- hexylene glycol double methacrylate), respectively at 50 DEG C, vacuum pressure takes off under conditions of being -0.095MPa
Except volatile organic matter 6 hours；
(2) production of ultraviolet-curing paint：It is gradually added into the light-initiated of the above-mentioned mixing of weight percent 5% in batches
The double propylene of agent, 40% epoxy acrylate, 30% urethane acrylate, 16% polyester acrylate and 10% tripropylene glycol
Acid esters stirs evenly at normal temperatures, you can.
The photocuring of coating：With UV curtain coaters on wood furniture surface the above-mentioned ultraviolet-curing paint of showering, wet coating thickness
About 30 μm~55 μm of degree, on the photo solidification machine of 2~5kw, with 0.1~1 m/min of speed, adjustment photocureable energy is about
80~400mJ/cm2, the coast of paint film of 25 μm~50 μm of UV light chemical conversion.Test the cured paint film of ultraviolet light photocuring it
To have certain taste afterwards, average conversion 89%, average gel rate (crosslinking ratio) is 85%, film thickness for 25 μm~
50 μm, paint film property is above standard the requirement in " ultraviolet light (UV) solidified carpentry coating HG/T 3655-2012 " to finishing coat.
The main performance of the paint film of the photocureable coating of embodiment and comparative example described in patent of the present invention is as shown in table 1.
Table 1
By embodiment 1-5 and table 1 as it can be seen that in the compound net taste photoinitiator of production zinc oxide and its ultraviolet light curing
During net taste coating, nano zine oxide is combined into novel inorganic/organic composite with polymerizable macromolecular photoinitiator
Net taste photoinitiator, after vacuum removal, without easy photodissociation, volatile organic low molecular compounds and activity dilution
Agent, net taste coating is after ultraviolet light curing, and paint film property is excellent and is net taste, average double bond conversion rate and gel fraction
It is all higher than 95%.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that those of ordinary skill in the art are come
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of compound net taste photoinitiator, which is characterized in that including following weight percentage components：
Zinc oxide 30~70%
Macromolecular photoinitiator 30~70%,
Wherein, the macromolecular photoinitiator is prepared by the acrylate of the photoinitiator of hydroxyl, isocyanates and hydroxyl
It forms.
2. compound net taste photoinitiator according to claim 1, which is characterized in that including following weight percent
Component：
Zinc oxide 45~55%
Macromolecular photoinitiator 45~55%.
3. compound net taste photoinitiator according to claim 1, which is characterized in that the zinc oxide is nano oxidized
Zinc, grain size are 10~200nm.
4. compound net taste photoinitiator according to claim 3, which is characterized in that the grain size of the zinc oxide is 20
~130nm.
5. according to the compound net taste photoinitiator of claim 1-4 any one of them, which is characterized in that the macromolecular light
Initiator is 1.05~1.1 by molar ratio:1:The acrylate system of the photoinitiator of 1 hydroxyl, isocyanates and hydroxyl
It is standby to form.
6. compound net taste photoinitiator according to claim 5, which is characterized in that the macromolecular photoinitiator
Preparation method includes the following steps：
By the crylic acid ester mixture of the isocyanates and hydroxyl, reacted 2~4 hours at 30~50 DEG C；It adds described
The photoinitiator of hydroxyl reacts 2~4 hours at 60~80 DEG C.
7. compound net taste photoinitiator according to claim 5, which is characterized in that the photoinitiator of the hydroxyl
For 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxycyclohexyl phenyl ketones, 2- hydroxyls -4'- (2- hydroxy ethoxies) -2-
One kind in methyl phenyl ketone；The isocyanates is isophorone diisocyanate；The acrylate of the hydroxyl is third
One kind in olefin(e) acid hydroxyl ethyl ester, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate.
8. a kind of ultraviolet-curing paint, which is characterized in that using any one of the claim 1-7 net taste photoinitiator conducts
Photoinitiator.
9. compound ultraviolet-curing paint according to claim 8, which is characterized in that by weight percentage, packet
Include the following raw material component：
10. the preparation method of the compound ultraviolet-curing paint described in claim 8 or 9, which is characterized in that including as follows
Step：
By the epoxy acrylate, urethane acrylate, polyester acrylate and reactive diluent respectively 50~80 DEG C,
Vacuum pressure pre-processes 3~6 hours under conditions of being -0.095MPa；
The pretreated epoxy acrylate, urethane acrylate, polyester acrylate and reactive diluent are mixed, with
And any one of claim 1-7 net taste photoinitiators, you can.
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| CN107337996A (en) * | 2017-07-21 | 2017-11-10 | 江苏宏泰高分子材料有限公司 | Solvent-free anti-corrosion of metal UV solidifications blacking of complete hiding and preparation method thereof |
| CN108409893B (en) * | 2018-03-07 | 2020-05-22 | 华南理工大学 | Surface modified nano ZnO photoinitiator and preparation method thereof |
| CN109705238B (en) * | 2018-12-19 | 2021-03-16 | 江苏乘鹰新材料股份有限公司 | Low-acetone-release low-mobility photoinitiator and preparation method and application thereof |
| CN112430279A (en) * | 2020-11-23 | 2021-03-02 | 濮阳展辰新材料有限公司 | Method for preparing macromolecular photoinitiator by acylation method and application thereof |
| CN112521579A (en) * | 2020-11-23 | 2021-03-19 | 青岛展辰新材料有限公司 | Synthesis and application of polyurethane type ultraviolet curing macroinitiator |
| CN112961266A (en) * | 2021-04-15 | 2021-06-15 | 惠州市红林实业有限公司 | Polymerizable photoinitiator, preparation method thereof and photocureable coating |
| CN114230747B (en) * | 2021-12-20 | 2024-02-02 | 江苏三木化工股份有限公司 | Preparation method of high-solid low-viscosity self-initiated epoxy acrylate oligomer |
| CN115140947B (en) * | 2022-09-05 | 2022-11-08 | 鼎钰玻璃(扬州)有限公司 | Coated photovoltaic glass and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993406A (en) * | 2012-12-12 | 2013-03-27 | 江南大学 | Preparation method of high-transparency UV resistant curing polyurethane-zinc oxide nano composite resin |
| CN103724556A (en) * | 2013-12-31 | 2014-04-16 | 蚌埠金黄山凹版印刷有限公司 | Preparation method of resin, resin, ink and preparation method thereof |
| CN104559386A (en) * | 2014-12-30 | 2015-04-29 | 青岛佳尚创意文化有限公司 | Water-based epoxy anti-corrosion coating |
| CN105255343A (en) * | 2015-11-17 | 2016-01-20 | 芜湖信宁新材料科技有限公司 | Nylon surface coating composition and preparation method of nylon surface coating |
| CN105778743A (en) * | 2014-12-22 | 2016-07-20 | 深圳市志邦科技有限公司 | Preparation method of LED white electrophoretic paint capable of dissipating heat and cooling through radiation |
| WO2016176270A1 (en) * | 2015-04-30 | 2016-11-03 | The Chemours Company Tt, Llc | Durable architectural coatings containing crosslinkable polymeric additives |
-
2016
- 2016-11-30 CN CN201611092888.1A patent/CN106632741B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993406A (en) * | 2012-12-12 | 2013-03-27 | 江南大学 | Preparation method of high-transparency UV resistant curing polyurethane-zinc oxide nano composite resin |
| CN103724556A (en) * | 2013-12-31 | 2014-04-16 | 蚌埠金黄山凹版印刷有限公司 | Preparation method of resin, resin, ink and preparation method thereof |
| CN105778743A (en) * | 2014-12-22 | 2016-07-20 | 深圳市志邦科技有限公司 | Preparation method of LED white electrophoretic paint capable of dissipating heat and cooling through radiation |
| CN104559386A (en) * | 2014-12-30 | 2015-04-29 | 青岛佳尚创意文化有限公司 | Water-based epoxy anti-corrosion coating |
| WO2016176270A1 (en) * | 2015-04-30 | 2016-11-03 | The Chemours Company Tt, Llc | Durable architectural coatings containing crosslinkable polymeric additives |
| CN105255343A (en) * | 2015-11-17 | 2016-01-20 | 芜湖信宁新材料科技有限公司 | Nylon surface coating composition and preparation method of nylon surface coating |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and property study of UV-curable hyperbranched polyurethane acrylate/ZnO hybrid coatings;Rama Shankar Mishra等;《European Polymer Journal》;20081127(第45期);第960–966页 * |
| UV固化有机/无机聚氨酯丙烯酸酯杂化材料合成研究进展;许雨晴 等;《中国胶粘剂》;20151231;第24卷(第12期);第56-59页 * |
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