CN107216776A - A kind of photo-thermal dual curable composition of insulating coating and its application - Google Patents
A kind of photo-thermal dual curable composition of insulating coating and its application Download PDFInfo
- Publication number
- CN107216776A CN107216776A CN201710411110.0A CN201710411110A CN107216776A CN 107216776 A CN107216776 A CN 107216776A CN 201710411110 A CN201710411110 A CN 201710411110A CN 107216776 A CN107216776 A CN 107216776A
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- China
- Prior art keywords
- photo
- curable composition
- insulating coating
- dual curable
- thermal dual
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- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000853 cresyl group Chemical class C1(=CC=C(C=C1)C)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- OCUJLLGVOUDECM-UHFFFAOYSA-N dipivefrin Chemical compound CNCC(O)C1=CC=C(OC(=O)C(C)(C)C)C(OC(=O)C(C)(C)C)=C1 OCUJLLGVOUDECM-UHFFFAOYSA-N 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LSWADWIFYOAQRZ-UHFFFAOYSA-N n-(ethoxymethyl)prop-2-enamide Chemical class CCOCNC(=O)C=C LSWADWIFYOAQRZ-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- NMHTWXYFOWTMJH-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(=O)OCC1CO1 NMHTWXYFOWTMJH-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N phenyldimethylamine Natural products CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-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
- 239000002689 soil Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/308—Wires with resins
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
- Organic Insulating Materials (AREA)
Abstract
The present invention relates to a kind of photo-thermal dual curable composition of insulating coating and its application.The light-cured resin of (A) containing carboxyl and unsaturated double-bond, (B) Photoepolymerizationinitiater initiater, (C) epoxy resin, (D) diluent, (E) epoxy hardener, (F) filler, (G) auxiliary agent are mainly contained in the photo-thermal dual curable composition of insulating coating.The photo-thermal dual curable composition of insulating coating of the present invention is based on the light-cured resin containing carboxyl and unsaturated double-bond, add filler, using the technique of photo-thermal dual curable, the coating of formation has a more preferable attachment in Copper base material, and the heat resistance of coating, hardness, scratch resistance have further raising.
Description
Technical field
The present invention relates to a kind of photo-thermal dual curable composition of insulating coating and its application.
Background technology
Insulated paint is to paint a kind of special varnish in class, is that based on high molecular polymer, can consolidate under certain conditions
It is melted into dielectric film or the overall important insulating materials of insulation.
Insulated paint is mainly used in wire enamel, and wire enamel is mainly used in the coating insulation of enamel-cover core.Due to wire
During coiling, rule etc., by the effect through heated, chemical and a variety of mechanical forces, therefore it is required that wire enamel has
Good coating (can uniformly coat), paint film adhesion is strong, smooth and soft surface flexible, there is certain wearability and bullet
Property, good electric property is heat-resisting, resistance to dissolubility, the characteristic such as corrosion-free to conductor.Traditional wire enamel is solvent-borne type, using thermosetting
The technique of change, a large amount of organic solvents, which are evaporate into air, during use causes environmental pollution, while consuming a large amount of heat energy, operates
Bad environments.
And though use photocuring insulated paint can solve the problems, such as the solvent discharge during use, light solidifying coating moment consolidates
Change internal stress larger, and most metals substrate surface has produced layer oxide film, the surface of metal oxide can be low, causes light
The coating material solidified poor adhesive force to metal base, and enamel-covered wire requires high to the adhesive force of paint film, while to there is good power
Learn and electric property.
The content of the invention
It is an object of the invention to provide a kind of photo-thermal dual curable composition of insulating coating and its application；The light of the present invention
High efficiency, the low solvent discharge of the hot existing photocuring insulated paint of dual cure composition of insulating coating, addition filler are favourable
In the internal stress for reducing coating instantaneous solidification, coating attachment is improved, the wearability and elasticity of coating, electric property is further improved
It is good, it is heat-resisting, the features such as solvent resistant.
The purpose of the present invention is achieved through the following technical solutions：
The present invention relates to a kind of photo-thermal dual curable composition of insulating coating, mainly contain (A) and contain carboxyl and unsaturation
The light-cured resin of double bond, (B) Photoepolymerizationinitiater initiater, (C) epoxy resin, (D) diluent, (E) epoxy hardener, (F) filler,
(G) auxiliary agent；
The parts by weight of each key component are respectively in the composition：
Wherein, the light-cured resin (A) containing carboxyl and unsaturated double-bond be molecule in contain at least two ends
The photoresist of ethylene type unsaturated bond, is synthesized by following any method：
(1) copolymer that (methyl) acrylic acid and other comonomer (a) reactions with ethylene type unsaturated bond are formed
Reacted with (methyl) glycidyl acrylate, the hydroxyl that reaction product is produced afterwards obtains synthetic resin with acid anhydrides (b) reaction；
(2) epoxide (c) and unsaturated monocarboxylic (d) with two or more epoxy radicals react in molecule, then
The hydroxyl that the reaction product is produced obtains synthetic resin with acid anhydrides (b) reaction；
(3) copolymerization of (methyl) glycidyl acrylate and other comonomers (a) with ethylene type unsaturated bond
Thing reacts with unsaturated monocarboxylic (d), and the hydroxyl that reaction product is produced afterwards obtains synthetic resin with acid anhydrides (b) reaction.
(methyl) acrylic acid and other comonomer (a) reaction shapes with ethylene type unsaturated bond in the above method (1)
Into the mol ratio of copolymer and (methyl) glycidyl acrylate be 0.2-1.2: 1, acid anhydrides (b) consumption is makes reaction
The solid constituent acid value of product is 50-150mgKOH/g consumption.
Mole of epoxide (c) and unsaturated monocarboxylic (d) in the above method (2) with two or more epoxy radicals
Than for 0.2-1.2: 1, acid anhydrides (b) consumption is to make the use that the solid constituent acid value of reaction product is 50-150mgKOH/g
Amount.
The above method (3) (methyl) glycidyl acrylate and other comonomers with ethylene type unsaturated bond
(e) copolymer is 0.2-1.2: 1 with unsaturated monocarboxylic (a) mol ratio, and acid anhydrides (b) consumption is to make reaction product
Solid constituent acid value is 50-150mgKOH/g consumption.
The example bag of workable other comonomers (a) with ethylene type unsaturated bond in the above method (1) and (3)
Include：Styrene, chlorostyrene, α-methylstyrene；By methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group,
Amino, 2- ethylhexyls, octyl group, caprinoyl, nonyl, decyl, dodecyl, cetyl, octadecyl, cyclohexyl, isoborneol
Base, methoxy ethyl, butoxyethyl group, 2- hydroxyethyls, 2- hydroxypropyls or the acrylate of 3- chlorine-2-hydroxyls propyl group substitution
Or methacrylate；The mono acrylic ester or monomethacrylates or the mono acrylic ester of polypropylene glycol of polyethylene glycol
Or monomethacrylates；Vinylacetate, vinyl butyrate or vinyl benzoate；Acrylamide, Methacrylamide, N-
Hydroxymethylacrylamide, N- methoxies acrylamide, N- ethoxymethyl acrylamides, N- butoxymethyl acryloyls
Amine, acrylonitrile or maleic anhydride etc..These comonomers (a) can be used alone that two or more may be used in combination.
The example of the acid anhydrides (b) used in the above method (1), (2), (3) includes：Maleic anhydride, succinic anhydride, itaconic acid
Acid anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl four
The dibasic acid anhydrides such as hydrogen phthalic anhydride；The aromatic series such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetrabasic carboxylic acid dicarboxylic anhydride
Polybasic acid anhydride；And 5- (2,5- dioxidotetrahydro furyl) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydrides, and it is similar
Polybasic acid anhydride derivative.These saturations or undersaturated multi-anhydride can be used in mixed way alone or in any combination.Consider
To the characteristic of paint base composition, tetrabydrophthalic anhydride, hexahydrophthalic anhydride and succinic anhydride are preferably used.
The example of workable epoxide (c) includes in the above method (2)：Bisphenol A type epoxy resin, A Hydrogenated Bisphenol A
A types epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, united phenol-type epoxy resin, di- toluene phenolic epoxy
Resin, triphenol methylmethane type epoxy resin and N- glycidyl type epoxy resins.Above-mentioned epoxide can be used alone
Two or more may be used in combination.Wherein, the novalac epoxies of the bisphenol-A in these epoxides, because it can
With obtain with adhesive force is good and the performance such as reagent resistance and preferably use.
The example of workable unsaturated monocarboxylic (d) includes in the above method (1), (3)：The two of acrylic acid, acrylic acid
Polymers, methacrylic acid, β-styrene acrylic, β-furfuryl acrylic acid, and saturation or unsaturated dicarboxylic acid anhydride and molecule
In (methyl) esters of acrylic acid containing a hydroxyl reactant or saturation or unsaturated dibasic acid single shunk with unsaturated
The esters of reactant half of glycerol compounds.In view of photo-curable, preferably used in these unsaturated monocarboxylics acrylic acid or
Methacrylic acid.
The light-cured resin containing carboxyl and unsaturated double-bond in photo-thermal dual curable Insulation primer composition of the present invention
(A) above-described material is not limited to, as long as there are at least two end ethylene type unsaturated bonds in molecule and have carboxyl
Resin can be used in the present invention.Above-mentioned substance can also be used in mixed way.
The light-cured resin (A) of carboxyl and unsaturated double-bond is preferably comprised in method (1), (2), (3) synthetic resin
Two or more is combined.
Further preferably the light-cured resin (A) of carboxyl and unsaturated double-bond is consolidated containing the light that reaction is obtained in method (1)
Change resin.The weight of obtained light-cured resin is reacted in light-cured resin (A) containing carboxyl and unsaturated double-bond in method (1)
It is preferably 25%-80% to measure content.Now, photo-thermal dual curable Insulation primer composition of the invention has optimal coating attached
Performance, its effect is no less than traditional heat cure insulated paint, is much better than photocuring insulated paint；Do not use organic solvent simultaneously,
Environmental-protecting performance is good.
Preferably, the photopolymerization light trigger is that benzoin, benzoin alkylether, acetophenones are light-initiated
At least one of agent, anthraquinone photoinitiator.
Preferably, the epoxy resin is bisphenol A type epoxy resin, bisphenol-A epoxy resin, Bisphenol F
The solvable epoxy resin of type epoxy resin, bisphenol-s epoxy resin, novolac epoxy resins, cresols, bisphenol-A it is solvable
Fusible epoxy resin, united phenol-type epoxy resin, di- toluene phenol-type epoxy resin, triphenol methylmethane type epoxy resin, N- contractings
Water glycerol type epoxy resin, three-glycidyl amines, 2,6- xylenols dimers diglycidyl ether, aliphatic epoxy
Resin, xylene epoxy resin.It is preferred that softening point is less than 60 DEG C of epoxy resin.
Preferably, the diluent can be the one or more in organic solvent, photo polymerization monomer.
The organic solvent be glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, DPG
The ethers such as monomethyl ether, DPE, Dipropylene glycol mono-n-butyl Ether；Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetic acid
Ester, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol ether acetate alone, diethylene glycol mono butyl
Ether acetate, propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetate, propyleneglycol monobutyl ether acetate, DPG list
The esters such as methyl ether acetate, DPE acetate, Dipropylene glycol mono-n-butyl Ether acetate；Conventional also has ketone molten
Agent, such as butanone, cyclohexanone, isophorone；Aromatic solvent, such as toluene, dimethylbenzene, durene；And oil series solvent, such as stone brain
Oil, aoxidizes naphtha, solvent naphtha etc..These solvents can be used in mixed way alone or in any combination.
More preferably diluent is photopolymerization monomer；The photo polymerization monomer is selected from simple function (methyl) acrylate, double
Function (methyl) acrylate, multifunctional (methyl) acrylate, ethoxylation polyfunctional acrylic ester, propoxylation are multifunctional
One or more of mixing in acrylate, (methyl) acrylate containing hydroxyl.Most preferably photo polymerization monomer is (first
Base) hydroxy-ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, 1,6- hexanediyl esters, tripropylene glycol diacrylate
One or both of.
Preferably, the epoxy hardener is imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2- ethyl -4- methyl
Imidazoles, 2- phenylimidazoles, 4- phenylimidazoles, 1- cyano ethyl -2- phenylimidazoles, 1- (2- cyano ethyls) -2- ethyl -4- methyl
The imdazole derivatives such as imidazoles；Dicyanodiamide, phenyl dimethyl amine, 4- (dimethylamino)-N, N- dimethyl benzyl amine etc.
Amines；The hydrazide kind compounds such as AH, decanedioyl hydrazine；Phosphorus compounds such as triphenyl phosphorus etc..Epoxy resin cure promotees
Enter agent and be not particularly limited in compound described above, as long as Epoxy cure catalysts, or promote epoxy radicals and carboxylic
The material of base reaction can be used in the present invention.Above-mentioned substance can be used in mixed way alone or in any combination.
Preferably, the filler both can be that inorganic filler may also be organic filler, and can be used alone also can two
Plant and the form of thing mixed above is used.Selected filler average grain diameter is at 1-10 microns, preferably 3-10 microns, and particle diameter too small is not
To the effect for reducing internal stress after curing of coatings, the insulating properties of the too big influence coating of particle diameter.Inorganic filler is silica flour, titanium dioxide
Silicon, barium sulfate, barium titanate, silicon oxide powder, talcum powder, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminium hydroxide, mica, height
Ridge soil；Organic filler can select polytetrafluorethylepowder powder, polyimide powder.
Preferably, the auxiliary agent is in levelling agent, defoamer, polymerization inhibitor, light-initiated auxiliary agent, adhesion promoter
One or more.
Paint is being prepared the invention further relates to a kind of a kind of photo-thermal dual curable composition of insulating coating as described in the present invention
Purposes in envelope curve.
The present invention is compared with conventional insulator paint technology, and the present invention has following beneficial effect：
1st, rapid curing, improves production efficiency；
2nd, using the technique of photo-thermal dual curable, composition addition filler advantageously reduces the planted agent of coating instantaneous solidification
Power, improves coating attachment；
3rd, composition addition filler is conducive to improving the characteristics such as heat-resisting coating, hardness, scratch resistance, insulation.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Term implication used herein is as follows：
" (methyl) acrylic acid " means the general name of acrylic acid, methacrylic acid and its mixture, other similar expressions
Implication is similar.
" ethylene type unsaturated bond ", which is meant, contains end-vinyl key in molecule.
Synthesis example 1
Light-cured resin A1 synthesis
In the reactor according to mol ratio for 1: 2: 1 ratio add methyl methacrylate, butyl methacrylate and
Acrylic acid, solvent uses diethylene glycol ether acetate, and initiator uses azodiisobutyronitrile (AIBN) (consumption 1%), 80
DEG C stirring 4 hours, obtain resin solution.
Using methylnaphthohydroquinone as polymerization inhibitor (consumption 0.5%), triphenylphosphine (consumption 1%) is as catalyst, in 90-95
Reacted under the conditions of DEG C with GMA, mole of the acrylic acid of GMA and the first step
Than for 1: 1, obtaining resin liquid.
The resin solution is cooled down, using methylnaphthohydroquinone (consumption 0.5%) as polymerization inhibitor, tetrabutyl phosphonium bromide phosphorus (consumption
1%) as catalyst, addition reaction, THPA and third in the first step are carried out with THPA under the conditions of 90-105 DEG C
The mol ratio of olefin(e) acid is 1: 1, and reaction is carried out 16 hours, takes out product resin liquid A1 after cooling.
Synthesis example 2
Light-cured resin A2 synthesis
100 grams of bisphenol A type epoxy resins (E51 resins, epoxide equivalent 200,0.50mol epoxy radicals) are added in the reactor
(production of Wuxi resin processing plant), 40 grams of acrylic acid (0.55mol), 0.5 gram of hydroquinones (polymerization inhibitor) and 2 grams of N, N- dimethylbenzyl ammonia
(catalyst), and in 95-98 DEG C of thermotonus 15 hours, its acid number is determined less than 3；Add 74 grams of phthalic anhydrides
(0.50mol) obtains the lurid resin liquid A2 that acid number is 61 in 90 DEG C of thermotonus 6 hours.
Synthesis example 3
Light-cured resin A3 synthesis
In the reactor GMA, methacrylic acid are added according to mol ratio for 1: 1: 1 ratio
Methyl esters and butyl methacrylate, solvent ethylene glycol ethyl ether acetate ester, initiator use azodiisobutyronitrile (consumption 1%),
80 DEG C are stirred 4 hours, obtain resin liquid.
The resin liquid is cooled down, using methylnaphthohydroquinone (consumption 0.5%) as polymerization inhibitor, triphenylphosphine (consumption 1%) conduct
Catalyst, with propylene acid reaction under the conditions of 90-95 DEG C, acrylic acid Glycidyl methacrylate used in being reacted with the first step is sweet
The mol ratio of grease is 1: 1, and reaction is carried out 16 hours, obtains resin liquid.
The resin solution is cooled down, using methylnaphthohydroquinone (consumption 0.5%) as polymerization inhibitor, tetrabutyl phosphonium bromide phosphorus (consumption
1%) as catalyst, addition reaction is carried out with hexahydrophthalic anhydride under the conditions of 90-105 DEG C, with hexahydro O-phthalic
The mol ratio of acid anhydrides and the acrylic acid in the first step is 1: 1, and reaction is carried out 16 hours, and resin liquid A3 is obtained after cooling.
Embodiment 1~6
Embodiment 1~6 each provides a kind of photo-thermal dual curable composition of insulating coating, the corresponding raw material of each composition
Component and part is as shown in table 1；
The corresponding raw material components of each embodiment are mixed by its parts by weight respectively, middling speed is scattered 2 hours, filtering is produced
A kind of corresponding photo-thermal dual curable composition of insulating coating.
Comparative example 1,2
Comparative example 1 and 2 respectively provides a kind of photo-thermal dual curable composition of insulating coating, and its preparation method includes following step
Suddenly：
(a) got the raw materials ready according to the component and part shown in table 1；
(b) raw material components are mixed, middling speed is scattered 2 hours, filtering produces a kind of photo-thermal dual curable coatings
Composition.
Table 1
Performance detection
In order to which the coating of the present invention and prior art are compared, it is coated in the following method, determines the flat of coating
Whole degree, adhesive force, fastness of aluminizing, specimen page outward appearance, heatproof.
First, outward appearance
Photo-thermal dual curable composition of insulating coating is coated with dip coating on copper cash after annealing, first using 300mJ/
cm2UV Light solidification, copper cash is put into 150 DEG C of baking ovens carries out solidify afterwards afterwards, finally estimate appearance of coat.
Evaluation method：Outward appearance has pin hole and scratch to be poor；Smooth in appearance is excellent without paint knurl.
2nd, electrical property
Photo-thermal dual curable composition of insulating coating is coated with dip coating on copper cash after annealing, according to method of testing
Technique in one makes test enamel-covered wire, takes enamel-covered wire 0.5m doublings once, and doubled over portion is cut and four line coat of paints are scraped off,
Enamel-covered wire after doubling is twisted into twisted shape, respectively with high pressure of the high pressure instrument test with one end both threads head.
Evaluation method：
Breakdown voltage is poor in below 2700V；
Breakdown voltage is good in 2700V-5000V；
Breakdown voltage is excellent in more than 5000V.
3rd, adhesive force
Test enamel-covered wire is made according to the technique in method of testing one, enamel-covered wire is examined with corresponding around Shang Shiquan
Paint film, which whether there is cracking, to come off.
Appraisal procedure：Do not ftracture and come off to be excellent completely, there is cracking to come off for difference.
4th, elongation
Test enamel-covered wire is made according to the technique in method of testing one, test enamel-covered wire is made, according to GBT4074.1-
2008 standards test extensibility using tensilometer.
Computational methods：Length before (length before the stretching of length one after stretching)/stretching
Appraisal procedure：Extensibility is excellent more than 30%, and extensibility is less than 30% to be poor.
5th, jerk disconnected
Jerked according to 2 meters per second of speed of GBT 4074.1-2008 standards, examine paint film whether there is cracking.
Appraisal procedure：It is excellent without cracking, ftractures as difference.
6th, thermal shock
It will wind enamel-covered wire according to GBT 4074.1-2008 standards and put and dry 0.5 hour in an oven, paint is examined after having dried
Film whether there is cracking.
Appraisal procedure：It is excellent without cracking, ftractures as difference.
Performance test results are as shown in table 2：
Table 2, performance detection situation
As shown in Table 2, a kind of photo-thermal dual curable composition of insulating coating made from embodiment 1~6 and comparative example 1~3
Photo-thermal dual curable composition of insulating coating compare：Composition prepared by embodiment is in outward appearance, electrical property, adhesive force, elongation
Rate, jerk disconnected, thermal shock in terms of performance protrude.
Comparative example 1-3 shows poor because not containing resin liquid A1 in terms of adhesive force, thermal shock test.
In summary, existing photocuring insulated paint during photo-thermal dual curable composition of insulating coating use of the invention
High efficiency, low solvent discharge, addition filler advantageously reduces the internal stress of coating instantaneous solidification, improves coating attachment,
The characteristics such as heat-resisting coating, hardness, scratch resistance, insulation are improved simultaneously.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. a kind of photo-thermal dual curable composition of insulating coating, it is characterised in that the weight of each key component in the composition
Number is respectively：
2. according to the photo-thermal dual curable composition of insulating coating described in claim 1, it is characterised in that it is described containing carboxyl and not
The light-cured resin of saturation double bond can be synthesized by following any method：
(1) (methyl) acrylic acid and other comonomer (a) reactions with ethylene type unsaturated bond are formed copolymer and (first
Base) glycidyl acrylate reaction, the hydroxyl that reaction product is produced afterwards reacts with acid anhydrides (b) obtains synthetic resin；
(2) epoxide (c) and unsaturated monocarboxylic (d) with two or more epoxy radicals react in molecule, and then this is anti-
The hydroxyl that product is produced is answered to obtain synthetic resin with acid anhydrides (b) reaction；
(3) copolymer of (methyl) glycidyl acrylate and other comonomers (a) with ethylene type unsaturated bond with
Unsaturated monocarboxylic (d) reacts, and the hydroxyl that reaction product is produced afterwards obtains synthetic resin with acid anhydrides (b) reaction.
3. photo-thermal dual curable composition of insulating coating according to claim 2, it is characterised in that in methods described (1)
Copolymer and (methyl) propylene that (methyl) acrylic acid and other comonomer (a) reactions with ethylene type unsaturated bond are formed
The mol ratio of acid glycidyl ester is 0.2-1.2: 1, and acid anhydrides (b) consumption is that the solid constituent acid value for making reaction product is
50-150mgKOH/g consumption.
4. photo-thermal dual curable composition of insulating coating according to claim 2, it is characterised in that in methods described (2)
The mol ratio of epoxide (c) and unsaturated monocarboxylic (d) with two or more epoxy radicals is 0.2-1.2: 1, the acid
Acid anhydride (b) consumption is to make the consumption that the solid constituent acid value of reaction product is 50-150mgKOH/g.
5. photo-thermal dual curable composition of insulating coating according to claim 2, it is characterised in that in methods described (3)
The copolymer of (methyl) glycidyl acrylate and other comonomers (a) with ethylene type unsaturated bond and unsaturation list
Carboxylic acid (d) mol ratio is 0.2-1.2: 1, and acid anhydrides (b) consumption is to make the solid constituent acid value of reaction product be 50-
150mgKOH/g consumption.
6. photo-thermal dual curable composition of insulating coating according to claim 2, it is characterised in that described contains carboxyl
It is that two or more in method (1), (2), (3) synthetic resin is combined with the light-cured resin of unsaturated double-bond.
7. photo-thermal dual curable composition of insulating coating according to claim 6, it is characterised in that described contains carboxyl
With the synthetic resin obtained in the light-cured resin of unsaturated double-bond containing the middle reaction of method (1).
8. photo-thermal dual curable composition of insulating coating according to claim 1, it is characterised in that the average grain of the filler
Footpath is 1~10 micron.
9. photo-thermal dual curable composition of insulating coating according to claim 1, it is characterised in that the filler is inorganic
Filler or organic filler；The inorganic filler is selected from silica flour, silica, barium sulfate, barium titanate, silicon oxide powder, talcum
Powder, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminium hydroxide, mica, kaolin；The organic filler is selected from polytetrafluoroethylene (PTFE)
Powder, polyimide powder.
10. it is a kind of as photo-thermal dual curable composition of insulating coating according to any one of claims 1 to 9 is preparing enamel-covered wire
In purposes.
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| CN109321024A (en) * | 2018-09-26 | 2019-02-12 | 上海乘鹰新材料有限公司 | A kind of cured photocuring heat cure Insulation primer composition of suitable LED and its preparation |
| CN111349215A (en) * | 2020-04-30 | 2020-06-30 | 西安天元化工有限责任公司 | Thermally initiated free radical reaction curing and conventional curing combined epoxy resin compositions |
| CN113416610A (en) * | 2021-06-18 | 2021-09-21 | 中国林业科学研究院林产化学工业研究所 | Light-cured resin based on vegetable oil and itaconic acid and preparation method and application thereof |
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| CN109321024A (en) * | 2018-09-26 | 2019-02-12 | 上海乘鹰新材料有限公司 | A kind of cured photocuring heat cure Insulation primer composition of suitable LED and its preparation |
| CN111349215A (en) * | 2020-04-30 | 2020-06-30 | 西安天元化工有限责任公司 | Thermally initiated free radical reaction curing and conventional curing combined epoxy resin compositions |
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