CN106221512A - Photocuring insullac compositions and the purposes in preparing enamel-covered wire thereof - Google Patents

Photocuring insullac compositions and the purposes in preparing enamel-covered wire thereof Download PDF

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Publication number
CN106221512A
CN106221512A CN201610607732.6A CN201610607732A CN106221512A CN 106221512 A CN106221512 A CN 106221512A CN 201610607732 A CN201610607732 A CN 201610607732A CN 106221512 A CN106221512 A CN 106221512A
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China
Prior art keywords
acid
photocuring
insullac
methyl
compositions
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Chinese (zh)
Inventor
虞明东
牛辉楠
季加进
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Shanghai Weikai Optoelectronic New Materials Co Ltd
Shanghai Chengying New Material Co Ltd
Jiangsu Chengying New Material Co Ltd
Original Assignee
Shanghai Weikai Optoelectronic New Materials Co Ltd
Shanghai Chengying New Material Co Ltd
Jiangsu Chengying New Material Co Ltd
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Application filed by Shanghai Weikai Optoelectronic New Materials Co Ltd, Shanghai Chengying New Material Co Ltd, Jiangsu Chengying New Material Co Ltd filed Critical Shanghai Weikai Optoelectronic New Materials Co Ltd
Priority to CN201610607732.6A priority Critical patent/CN106221512A/en
Publication of CN106221512A publication Critical patent/CN106221512A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
    • C08G59/1422—Polycondensates modified by chemical after-treatment with inorganic compounds containing phosphorus
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
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    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • H01B3/44—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 vinyl resins; acrylic resins
    • H01B3/447—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 vinyl resins; acrylic resins from acrylic compounds
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
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    • C08F2810/00—Chemical modification of a polymer
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    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract

The present invention relates to a kind of photocuring insullac compositions and the purposes in preparing enamel-covered wire thereof.This photocuring insullac compositions mainly contains molecule has the light-cured resin of phosphate ester structure, trigger for optical solidification, photo-curing monomer.The photocuring insullac compositions of the present invention introduces the light-cured resin containing phosphate, because phosphate can produce slight erosion to Copper base material, and form chelation structure on copper surface, and then it is effectively increased the attachment on copper cash of the photocuring insullac so that its good attachment on copper cash is not easily stripped.

Description

Photocuring insullac compositions and the purposes in preparing enamel-covered wire thereof
Technical field
The present invention relates to light-cured resin field, be specifically related to a kind of photocuring insullac compositions and preparing enamel-cover Purposes in line.
Background technology
Insullac is a kind of special varnish of paint apoplexy due to endogenous wind, is based on high molecular polymer, can consolidate under certain conditions Chemical conversion dielectric film or the important insulant of insulation entirety.
Insullac 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 through being heated, the effect of chemical and multiple mechanical force, therefore it is required that wire enamel has Good coating (can uniformly coat), paint film adhesion is strong, and smooth and soft surface flexible has certain wearability and bullet Property, good electric property, heat-resisting, resistance to dissolubility, to the characteristic such as conductor is corrosion-free.Traditional wire enamel is solvent-borne type, uses thermosetting The technique changed, during use, a large amount of organic solvents evaporate in air and cause environmental pollution, consume a large amount of heat energy simultaneously, operation Bad environments.
More existing employing photocuring insullac substitute traditional heat cure insullac, but photocuring insullac is because using purple Outer illumination instantaneous solidification, in causing paint film, molecule stress cannot discharge, paint film at the adhesive force of copper cash than traditional heat cure Insullac is poor, easily peels off from copper cash.
Summary of the invention
It is an object of the invention to overcome existing photocuring insullac more exhausted than traditional heat cure at the adhesive force of copper cash Edge paint is poor, the defect easily peeled off from copper cash, it is provided that a kind of photocuring insullac compositions and in preparing enamel-covered wire Purposes.
Term implication used herein is as follows:
" (methyl) acrylic acid " means the general name of acrylic acid, methacrylic acid and its mixture, other similar expression Implication is similar.
It is an object of the invention to be achieved through the following technical solutions:
The present invention relates to a kind of photocuring insullac compositions, mainly contain the photocuring in molecule with phosphate ester structure Resin, trigger for optical solidification and photo-curing monomer.
Preferably, described molecule has the product that one of below the light-cured resin of phosphate ester structure a-f reaction obtains Or any mixture of product that a-f reaction obtains:
In a, a molecule epoxy resin containing two and plural epoxy radicals successively with (methyl) acrylic acid, five Aoxidize the product that two phosphorus reactions obtain；
The epoxy resin of b, glycidyl methacrylate and simple function unsaturated compound copolymerization, more successively with propylene Acid, phosphorus pentoxide react the product obtained；
Containing two and the epoxy resin of plural epoxy radicals and a molecule contain two carboxylics in c, a molecule The acid of base carries out chain extending reaction, then reacts, with (methyl) acrylic acid, phosphorus pentoxide, the product obtained；
In d, a molecule, the epoxy resin containing two and plural epoxy radicals reacts chain extension with multi-anhydride, then The product obtained is reacted with (methyl) acrylic acid, phosphorus pentoxide；
In e, a molecule, the epoxy resin containing two and plural epoxy radicals is anti-with aliphatic primary amine/secondary amine Answer chain extension, then react, with (methyl) acrylic acid, phosphorus pentoxide, the product obtained；
Containing two and the epoxy resin of plural epoxy radicals and phosphorus oxychloride reaction in f, a molecule, then with (methyl) acrylic acid reacts the product obtained.
Preferably, in said method, the example of spendable epoxy resin includes: bisphenol A type epoxy resin, hydrogenated bisphenol A The solvable epoxy of type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, novolac epoxy resins, cresol Resin, the novalac epoxies of bisphenol-A, united phenol-type epoxy resin, di-toluene phenol-type epoxy resin, triphenol methylmethane Type epoxy resin and N-(+)-2,3-Epoxy-1-propanol type epoxy resin.Above-mentioned epoxide can be used alone and can also two or more mix Use.
Preferably, in said method, the example of simple function unsaturated compound includes: styrene, chlorostyrene, Alpha-Methyl Styrene；By methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amino, 2-ethylhexyl, octyl group, the last of the ten Heavenly stems Acyl, nonyl, decyl, dodecyl, cetyl, octadecyl, cyclohexyl, isobornyl, methoxy ethyl, butoxy second Base, 2-hydroxyethyl, 2-hydroxypropyl and the substituted acrylate of 3-chlorine-2-hydroxyl propyl group or methacrylate；Poly-second two The mono acrylic ester of alcohol or monomethacrylates or the mono acrylic ester of polypropylene glycol or monomethacrylates；Acetic acid Vinyl acetate, vinyl butyrate or vinyl benzoate；Acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-first Epoxide Methacrylamide, N-ethoxymethyl acrylamide, N-butoxy methyl acrylamide, acrylonitrile or maleic anhydride Deng.These simple function unsaturated compounds can be used alone that two or more may be used in combination.
Preferably, in said method, in a spendable molecule, the example of acid containing two carboxyls includes: ethanedioic acid, third Diacid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, SA, 2,3 dihydroxybutanedioic acid, maleic Diacid, ricinoleic acid, oleic acid, linoleic acid etc..It is a discovery of the invention that introduce long flexible chain in the composition system of the present invention, improve The attachment of resin flexible toughness, beneficially end formulation and pliable and tough；Therefore, more preferably use maleic acid, ricinoleic acid, oleic acid, Linoleic acid.
Preferably, in said method, the example of spendable multi-anhydride includes: maleic anhydride, succinic anhydrides, itaconic acid Acid anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methano- Interior-tetrabydrophthalic anhydride, methyl methano-interior-binary acid such as tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride Acid anhydride；The aromatic polycarboxylic acid acid anhydrides such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetrabasic carboxylic acid dicarboxylic anhydride；And 5-(2,5- Dioxidotetrahydro furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and similar polybasic acid anhydride derivant.This The most saturated or undersaturated multi-anhydride can be used in mixed way alone or in any combination.In view of the characteristic of cured coating film, mainly It is easy to get from improving resin thermostability/material and from the standpoint of cost etc., more preferably uses tetrabydrophthalic anhydride, hexahydro neighbour's benzene Dicarboxylic acid anhydride and succinic anhydrides.
Preferably, described trigger for optical solidification is benzoin, benzoin alkylether, acetophenones light trigger, Anthraquinones Light trigger, thiaxanthone photoinitiator, ketal photoinitiator, organic peroxide, mercaptan compound, organohalogen compounds, Benzophenones light trigger, 2,4,6-trimethyl benzoyl diphenyl base phosphorous oxides, double [the fluoro-3-of 2,6-bis-(1H-pyrrole radicals- 1) phenyl] titanium luxuriant, double (pentafluorophenyl group) titanium cyclopentadienyl, anthraquinone/tertiary amine light initiation system, camphorquinone/tertiary amine light initiation system, 3-ketone group Coumarin/tertiary amine light initiation system, 2-methyl isophthalic acid-[4-(methyl thio) phenyl]-2-morpholinopropanone-1,2-benzyl-2-two The mixing of one or more in methylamino-1-(4-morpholino phenyl)-butane-1-ketone.It is easy to get from material and examines cost Consider,More preferablyDescribed uv photopolymerization light trigger is benzoin, benzoin alkylether, acetophenones light trigger, Anthraquinones At least one in light trigger.
Preferably, described photo-curing monomer is simple function (methyl) acrylate, difunctionality (methyl) acrylate, many officials Can (methyl) acrylate, ethoxylation polyfunctional acrylic ester, propoxylation polyfunctional acrylic ester, (first containing hydroxyl Base) mixing of one or more in acrylate.It is highly preferred that described photo polymerization monomer is (methyl) acrylic acid-2-hydroxyl second One or two in ester, (methyl) 2-hydroxypropyl acrylate, 1,6 hexanediol diacrylate, tripropylene glycol diacrylate Kind.It has furthermore been found that in the composition system of the present invention, (methyl) acrylic acid-2-hydroxyl ethyl ester contains hydroxyl and is particularly advantageous in Formula attachment in Copper base material, therefore, the most preferably combination of (methyl) acrylic acid-2-hydroxyl ethyl ester；The most described photopolymerization Monomer is (methyl) acrylic acid-2-hydroxyl ethyl ester, or be (methyl) acrylic acid-2-hydroxyl ethyl ester with (methyl) 2-hydroxypropyl acrylate, 1,6 hexanediol diacrylate or the mix monomer of tripropylene glycol diacrylate.
Preferably, described light curing resin composition possibly together with auxiliary agent, described auxiliary agent be levelling agent, defoamer, polymerization inhibitor, One or more in light-initiated auxiliary agent, adhesion promoter.
Preferably, the parts by weight of described each component are respectively as follows:
The invention still further relates to a kind of aforesaid photocuring insullac compositions and prepare the purposes of enamel-covered wire.
Compared with prior art, there is advantages that
1, the light-cured resin containing phosphate is introduced, because phosphate can produce slight erosion to Copper base material, and at copper table Face forms chelation structure, and then is effectively increased the attachment on copper cash of the photocuring insullac；
2, the photocuring insullac compositions Light-Curing Efficiency of the present invention is high, it is possible to significantly improve production efficiency；Meanwhile, also There is the advantages such as solvent-free volatilization, environmental protection.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in the technology of this area Personnel are further appreciated by the present invention, but limit the present invention the most in any form.It should be pointed out that, the ordinary skill to this area For personnel, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement.These broadly fall into the present invention Protection domain.
Embodiment 1
Molecule has the synthesis of the light-cured resin A1 of phosphate ester structure
Add in the reactor 100 grams of bisphenol A type epoxy resins (E51 resin, epoxide equivalent 200), 40 grams of acrylic acid, 0.5 gram of hydroquinone (polymerization inhibitor) and 2 grams of-N, N-dimethylbenzyl ammonia (catalyst), and little the thermotonus 15 of 95-98 DEG C Time, measure its acid number less than 3.
Afterwards temperature of charge is down to room temperature, uses ice bath control temperature of charge at 0-10 DEG C, add phosphorus pentoxide 5g, Stirring reaction 5h, is warmed up to 60-65 DEG C of reaction 3h afterwards, obtains brown color resin liquid A1.
Prepare photocuring insullac compositions, take the light-cured resin A1 in above-mentioned molecule with phosphate ester structure, other Corresponding raw material components and parts by weight are as shown in table 1, mix by its parts by weight, and middling speed is disperseed 2 hours, filter, and it is right to obtain A kind of photocuring insullac compositions answered.
Embodiment 2
Molecule has the synthesis of the light-cured resin A2 of phosphate ester structure
Add in the reactor 200 grams of bisphenol A type epoxy resins (E20 resin, epoxide equivalent 500), 28.8 grams of acrylic acid, 0.5 gram of hydroquinone (polymerization inhibitor) and 2 grams of triphenylphosphines (catalyst), and the thermotonus 15 hours of 95-98 DEG C, measure it Acid number is less than 3.Afterwards temperature of charge is down to room temperature, uses ice bath control temperature of charge at 0-10 DEG C, add 6g five and aoxidize two Phosphorus, stirring reaction 5h, it is warmed up to 60-65 DEG C of reaction 3h afterwards, obtains brown color resin liquid A2.
Prepare photocuring insullac compositions, take the light-cured resin A2 in above-mentioned molecule with phosphate ester structure, other Corresponding raw material components and parts by weight are as shown in table 1, mix by its parts by weight, and middling speed is disperseed 2 hours, filter, and it is right to obtain A kind of photocuring insullac compositions answered.
Embodiment 3
Molecule has the synthesis of the light-cured resin A3 of phosphate ester structure
Glycidyl methacrylate, methacrylic acid is added in the reactor according to the ratio that mol ratio is 1:1:1 Methyl ester and butyl methacrylate, initiator uses azodiisobutyronitrile (AIBN), stirs 4 hours at 80 DEG C, obtains resin liquid.
Cooling down this resin liquid, use methylnaphthohydroquinone as polymerization inhibitor, triphenylphosphine is as catalyst, 90-95 DEG C of condition Reacting with acrylic acid down, the mol ratio of the glycidyl methacrylate that acrylic acid is used in reacting with the first step is 1:1, instead Should carry out 10 hours.
Afterwards temperature of charge is down to room temperature, uses ice bath to control temperature of charge at 0-10 DEG C, add phosphorus pentoxide, five Aoxidizing the mol ratio that two phosphorus and the first step react glycidyl methacrylate is 1:4, and stirring reaction 5h is warmed up to afterwards 60-65 DEG C of reaction 3h, obtains brown color resin liquid A3.
Prepare photocuring insullac compositions, take the light-cured resin A3 in above-mentioned molecule with phosphate ester structure, other Corresponding raw material components and parts by weight are as shown in table 1, mix by its parts by weight, and middling speed is disperseed 2 hours, filter, and it is right to obtain A kind of photocuring insullac compositions answered.
Embodiment 4
Molecule has the synthesis of the light-cured resin A4 of phosphate ester structure
Add Phosphorous chloride. and epoxy resin according to the ratio that mol ratio is 1:8 in the reactor, stir at normal temperatures Reaction 6h, obtains yellowish-brown resin liquid.At 90 DEG C, drip acrylic acid according to the mol ratio of 1:3 and react in this resin liquid, The product A4 arrived.
Prepare photocuring insullac compositions, take the light-cured resin A4 in above-mentioned molecule with phosphate ester structure, other Corresponding raw material components and parts by weight are as shown in table 1, mix by its parts by weight, and middling speed is disperseed 2 hours, filter, and it is right to obtain Should a kind of photocuring insullac compositions.
Embodiment 5-6
Prepare photocuring insullac compositions, according to the most corresponding raw material components and parts by weight, by its weight Number mixes, and middling speed is disperseed 2 hours, filters, obtains corresponding a kind of photocuring insullac compositions.
Comparative example 1-2
The synthesis of epoxy acrylic resin A5
Add in the reactor 100 grams of bisphenol A type epoxy resins (E51 resin, epoxide equivalent 200), 36 grams of acrylic acid, 0.5 gram of hydroquinone and 2 grams of N, N-dimethylbenzyl ammonia, and the thermotonus 15 hours of 95-98 DEG C, measure its acid number less than 3. Obtain lurid resin liquid A5.
Preparing photocuring insullac compositions, take above-mentioned resin liquid A5, the raw material components of other correspondence and parts by weight are such as Shown in table 1, mixing by its parts by weight, middling speed is disperseed 2 hours, filters, obtains corresponding a kind of photocuring insullac compositions.
Table 1
Performance detects
In order to the coating of the present invention with prior art compares, it is coated in the following method, measures the flat of coating Whole degree, adhesive force, fastness of aluminizing, specimen page outward appearance, heatproof.
One, outward appearance
With dip coating, photocuring insullac compositions is coated with on copper cash after annealing, uses 300mJ/cm2Ultraviolet Light illumination curing, then estimates appearance of coat.
Evaluation methodology: outward appearance has pin hole and scratch for poor；Smooth in appearance is excellent without paint tumor.
Two, electrical property
With dip coating, photocuring insullac compositions is coated with on copper cash after annealing, makes test enamel-covered wire, take paint Doubled over portion once, is cut off and is scraped off four line coat of paints, the enamel-covered wire after doubling is twisted into twisted shape by envelope curve 0.5m doubling, point Yong not test the high pressure with one end both threads head by high pressure instrument.
Evaluation methodology:
Breakdown voltage is poor at below 2700V；
Breakdown voltage is good at 2700V-5000V；
Breakdown voltage is excellent at more than 5000V.
Three, adhesive force
With knife coating by coatings copper cash after annealing, make test enamel-covered wire, by enamel-covered wire with corresponding Around Shang Shiquan, inspection paint film comes off with or without cracking.
Appraisal procedure: come off for excellent entirely without cracking, has cracking to come off for difference.
Four, percentage elongation
With dip coating, photocuring insullac compositions is coated with on copper cash after annealing, makes test enamel-covered wire, according to GBT4074.1-2008 standard uses tensilometer test extensibility.
Computational methods: the length before (length before length-stretching after stretching)/stretching
Appraisal procedure: extensibility is excellent more than 30%, extensibility is poor less than 30%.
Five, jerk is disconnected
Jerking according to the speed of 2 meters per second of GBT 4074.1-2008 standard, inspection paint film is with or without cracking.
Appraisal procedure: without cracking for excellent, ftracture as difference.
Six, thermal shock
According to GBT 4074.1-2008 standard, winding enamel-covered wire is put baking 0.5 hour in an oven, after having dried, check paint Film is with or without cracking.
Appraisal procedure: without cracking for excellent, ftracture as difference.
Performance test results is as shown in table 2:
Table 2, performance detection case
As shown in Table 2, comparative example 1-2 comprises only epoxy acrylic resin and does not contains in molecule the light with phosphate ester structure Solidification resin is poor in adhesive force, test of elongation rate performance.A kind of photocuring insullac compositions that embodiment 1～6 prepares is with right The photocuring insullac compositions of ratio 1～2 is compared: compositions prepared by embodiment adhesive force outside, percentage elongation aspect performance Prominent.Analyze its reason, it may be possible to the photocuring insullac compositions of the present invention introduces the light-cured resin containing phosphate, Wherein phosphate can produce slight erosion to Copper base material, and form chelation structure on copper surface, and then it is exhausted to be effectively improved photocuring The attachment on copper cash of the edge paint.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformation or amendment within the scope of the claims, this not shadow Ring the flesh and blood of the present invention.

Claims (10)

1. a photocuring insullac compositions, mainly contains and has the light-cured resin of phosphate ester structure, photocuring in molecule Initiator and photo-curing monomer.
Photocuring insullac compositions the most according to claim 1, it is characterised in that there is in described molecule phosphate ester knot Any mixture of the product that the light-cured resin of structure is the product that obtains of one of following a-f reaction or a-f reaction obtains:
In a, a molecule epoxy resin containing two and plural epoxy radicals successively with (methyl) acrylic acid, five oxidations The product that two phosphorus reactions obtain；
The epoxy resin of b, glycidyl methacrylate and simple function unsaturated compound copolymerization, more successively with acrylic acid, Phosphorus pentoxide reacts the product obtained；
Containing two and the epoxy resin of plural epoxy radicals and a molecule contain two carboxyls in c, a molecule Acid carries out chain extending reaction, then reacts, with (methyl) acrylic acid, phosphorus pentoxide, the product obtained；
In d, a molecule, epoxy resin containing two and plural epoxy radicals and multi-anhydride react chain extension, then with (methyl) acrylic acid, phosphorus pentoxide react the product obtained；
In e, a molecule, the epoxy resin containing two and plural epoxy radicals reacts expansion with aliphatic primary amine/secondary amine Chain, then react, with (methyl) acrylic acid, phosphorus pentoxide, the product obtained；
Containing two and the epoxy resin of plural epoxy radicals and phosphorus oxychloride reaction in f, a molecule, then with (methyl) Acrylic acid reacts the product obtained.
Photocuring insullac compositions the most according to claim 2, it is characterised in that described simple function unsaturated compound The mixing of one or more in following material: styrene, chlorostyrene, α-methyl styrene, by methyl, ethyl, propyl group, Isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amino, 2-ethylhexyl, octyl group, caprinoyl, nonyl, decyl, dodecyl, 16 Alkyl, octadecyl, cyclohexyl, isobornyl, methoxy ethyl, butoxyethyl group, 2-hydroxyethyl, 2-hydroxypropyl or 3- The substituted acrylate of chlorine-2-hydroxyl propyl group or methacrylate, the mono acrylic ester of Polyethylene Glycol, single first of Polyethylene Glycol Base acrylate, the mono acrylic ester of polypropylene glycol, the monomethacrylates of polypropylene glycol, vinylacetate, butanoic acid ethylene Ester, vinyl benzoate, acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-methoxy acryloyl Amine, N-ethoxymethyl acrylamide, N-butoxy methyl acrylamide, acrylonitrile, maleic anhydride.
Photocuring insullac compositions the most according to claim 2, it is characterised in that containing two carboxylics in one molecule The acid of base includes: ethanedioic acid, malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, SA, 2, One or more in 3-dyhydrobutanedioic acid, maleic acid, ricinoleic acid, oleic acid, linoleic acid.
Photocuring insullac compositions the most according to claim 2, it is characterised in that described multi-anhydride includes following thing One or more in matter: maleic anhydride, succinic anhydrides, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, six Hydrogen phthalic anhydride, methylhexahydrophthalic anhydride, methano-interior-tetrabydrophthalic anhydride, methyl methano-interior-tetrahydrochysene Phthalic anhydride, methyl tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetrabasic carboxylic acid diacid Acid anhydride, 5-(2,5-dioxidotetrahydro furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.
Photocuring insullac compositions the most according to claim 1, it is characterised in that described trigger for optical solidification is that benzene is even Relation by marriage, benzoin alkylether, acetophenones light trigger, Anthraquinones light trigger, thiaxanthone photoinitiator, ketal class are light-initiated Agent, organic peroxide, mercaptan compound, organohalogen compounds, Benzophenones light trigger, 2,4,6-trimethylbenzoyl two Phenyl phosphorous oxides, double [the fluoro-3-of 2,6-bis-(1H-pyrrole radicals-1) phenyl] titanium luxuriant, double (pentafluorophenyl group) titanium cyclopentadienyl, anthraquinone/tertiary amine Light initiation system, camphorquinone/tertiary amine light initiation system, 3-ketocoumarin/tertiary amine light initiation system, 2-methyl isophthalic acid-[4-(first Base sulfur generation) phenyl]-2-morpholinopropanone-1, in 2-benzyl-2-dimethyl amido-1-(4-morpholino phenyl)-butane-1-ketone The mixing of one or more.
Photocuring insullac compositions the most according to claim 1, it is characterised in that described photo-curing monomer is simple function (methyl) acrylate, difunctionality (methyl) acrylate, multifunctional (methyl) acrylate, the multifunctional acrylic acid of ethoxylation The mixing of one or more in ester, propoxylation polyfunctional acrylic ester, (methyl) acrylate containing hydroxyl.
Photocuring insullac compositions the most according to claim 1, it is characterised in that possibly together with auxiliary agent, described auxiliary agent is One or more in levelling agent, defoamer, polymerization inhibitor, light-initiated auxiliary agent, adhesion promoter.
9. according to the photocuring insullac compositions according to any one of claim 1～9, it is characterised in that described photocuring In resin combination, the parts by weight of each component are respectively as follows:
10. a photocuring insullac compositions according to claim 1 is preparing the purposes of enamel-covered wire.
CN201610607732.6A 2016-07-28 2016-07-28 Photocuring insullac compositions and the purposes in preparing enamel-covered wire thereof Pending CN106221512A (en)

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