CN105968334A - Polyfunctional light-cured resin for color photoresistance and preparation method thereof - Google Patents
Polyfunctional light-cured resin for color photoresistance and preparation method thereof Download PDFInfo
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- CN105968334A CN105968334A CN201610327811.1A CN201610327811A CN105968334A CN 105968334 A CN105968334 A CN 105968334A CN 201610327811 A CN201610327811 A CN 201610327811A CN 105968334 A CN105968334 A CN 105968334A
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
- C08G63/21—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
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Abstract
The invention discloses polyfunctional light-cured resin for color photoresistance. The polyfunctional light-cured resin is prepared by carrying out partial esterifying reaction on biological polyhydric alcohol and acid anhydride containing a benzene ring rigid structure, and then carrying out secondary esterification or interesterification with hydroxyalkyl methacrylate. The resin has the advantages of good hydrophobicity, high hardness of products when applied to color photoresistance, excellent heat resistance, aging resistance and chemical resistance, low preparation cost, simple operation and high product yield.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of many officials for chromatic photoresist
Energy degree light-cured resin and preparation method thereof.
Background technology
Acrylics monomer is the type free base initiation that UV curing field is most-often used
Polymerization activity monomer, has the features such as viscosity is low, reactivity is high, quick solidifying, by increasing
Degree of functionality, can further improve its crosslink density and reaction rate.But, increase degree of functionality and lead to
System viscosity often can be caused to increase, and coating volume contraction is aggravated, and easily causes loss of adhesion, resistance to
Degradation defect under water weatherability.On the other hand, the synthesis of acrylics monomer is used mostly stone
Oil industrial chemicals, belongs to non-renewable resources, and easily environment is produced pollution.At synthon
During be increasingly introducing the environmentally friendly bio-based macromolecule belonging to natural reproducible resource
Material, to synthesize substituted type or the more excellent photocuring activated monomer of performance, has important reality
It is worth and wide development space, is also a focus of this area research and development.
Summary of the invention
It is an object of the invention to provide a kind of polyfunctionality photocuring tree for chromatic photoresist
Fat.This resin hydrophobic is good, and after being applied to chromatic photoresist, product hardness is high, has excellence
Thermostability, resistance to ag(e)ing and resistance to chemical corrosion, and its preparation cost is low, it is easy and simple to handle,
Product yield is high.
To achieve these goals, the present invention, from Molecular Design, utilizes and belongs to natural
The environmentally friendly biological multielement alcohol of Renewable resource and the anhydride containing phenyl ring rigid structure are carried out
Partial esterification reacts, and then carries out secondary esterification with (methyl) acrylic acid hydroxy alkyl ester or ester is handed over
Change, obtain required resin.
Specifically, the preparation side of a kind of polyfunctionality light-cured resin for chromatic photoresist
Method, comprises the following steps:
(1) by natural polyols and anhydride with the mixed in molar ratio of 1:1-5, make at catalyst
In organic solvent, carry out esterification under with, obtain intermediate product；
Described natural polyols is selected from gallic acid, sucrose, cyclodextrin or glucose, described acid
Acid anhydride is selected from pyromellitic dianhydride, trimellitic anhydride, the double phthalic anhydride of 4,4'-oxygen, adjacent benzene two
Formic anhydride or phenylsuccinic acid acid anhydride；
(2) intermediate product mixes with (methyl) acrylic acid hydroxy alkyl ester, in catalyst and resistance
Carry out esterification under poly-agent existence condition, obtain product.
The organic solvent kind used in step (1) is not particularly limited, as long as can be molten
Solve reaction raw materials and reaction is had no adverse effects, can be such as acetone, toluene, benzene,
Thiacyclohexane etc..Use catalyst can be hydrochloric acid, sulphuric acid, p-methyl benzenesulfonic acid, oxalic acid, three
One or more combination in boron fluoride, anhydrous Aluminum chloride or zinc chloride, consumption is preferred
0.1-5wt% for reaction raw materials.Reaction temperature is adjusted according to raw material type, usually
60-110℃。
In step (2), the amount of (methyl) acrylic acid hydroxy alkyl ester is preferably intermediate product
5-30wt%.This reaction can be carried out in the case of solvent-free participation, makes middle product after heating
Thing fusing can play the effect of reaction carriers, and heating-up temperature generally can be 200-250 DEG C.Make
Catalyst can be hydrochloric acid, sulphuric acid, p-methyl benzenesulfonic acid, oxalic acid, boron trifluoride, anhydrous
One or more combination in aluminum chloride or zinc chloride, consumption is preferably intermediate product
0.1-5wt%.The polymerization inhibitor used can be hydroquinone, 1,4-benzoquinone, phenothiazine, beta-phenyl
One or more combination in naphthylamines, p-tert-Butylcatechol, during consumption is preferably
Between the 0.5-2wt% of product.For controlling response speed, can first intermediate product be mixed with catalyst,
Then add by the way of dropping after (methyl) acrylic acid hydroxy alkyl ester being mixed with polymerization inhibitor
Reaction system.
With above-mentioned preparation method accordingly, the invention still further relates to be prepared many by above-mentioned preparation method
Degree of functionality light-cured resin and the application in chromatic photoresist thereof.
The present invention is with natural polyols, containing phenyl ring anhydride, (methyl) acrylic acid hydroxy alkyl ester be
Raw material, has synthesized the polyfunctionality light-cured resin containing natural macromolecular and phenyl ring rigid structure.
This resinoid photolytic activity is good, and efficiency of initiation is high, and when photocuring, volume contraction is less, it is possible to make
Polymer has preferable hardness, hydrophobicity and a heat resistance, and resistance to ag(e)ing and chemically-resistant rotten
Erosion excellent performance, has a wide range of applications in preparing chromatic photoresist product scope.
Detailed description of the invention
Below in conjunction with specific embodiment to further describe the present invention, but it is not intended to the present invention
Scope.
Preparation embodiment
Embodiment 1:
(1) in the 250mL four-hole boiling flask be furnished with agitating device, thermometer and condensing tube by
Mol ratio 1:1 adds gallic acid, pyromellitic dianhydride, and accounts for the salt of reactant 5wt%
Acid (concentration 37wt%, as follows), with acetone as reaction dissolvent, is heated to 60 DEG C and condenses back
Stream.Every 30min sampling esterification yield by infrared analysis pyromellitic dianhydride.Treat that anhydride exists
1847cm-1The infrared peak at place is decreased to no longer change, 3600cm simultaneously-1Hydroxyl peak also subtract
Little to no longer changing, show fully to react.Reduce pressure distilling off solvent subsequently, obtains pressed powder
Product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.005g hydrochloric acid, start stirring after being heated to fusing, when system temperature rises to 200 DEG C,
Dropping 0.5g methacrylate (containing 0.05g hydroquinone), rate of addition is with temperature
Inconspicuous decline is as the criterion, and is warming up to 220 DEG C after adding, and keeps constant temperature in course of reaction.Every
10min sampling and measuring infrared spectrum, 1650cm-1Occur that acrylic double bond peak to double bond peak increases
To no longer changing, observing response situation, arrive viscosity very big after stopped reaction, cooling while hot
Pour out product, obtain yellow solid.
Embodiment 2:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:5 adds gallic acid, pyromellitic dianhydride, and accounts for the salt of reactant 0.1wt%
Acid, with acetone as reaction dissolvent, is heated to 60 DEG C of condensing refluxes.Every 30min sampling is passed through
Infrared analysis pyromellitic dianhydride esterification yield.Treat that anhydride is at 1847cm-1The infrared peak at place reduces
To no longer changing, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer change, show fully
After reaction, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.005g hydrochloric acid, start stirring after being heated to fusing, when system temperature rises to 200 DEG C,
Dropping 0.5g methacrylate (containing 0.05g hydroquinone), rate of addition is with temperature
Inconspicuous decline is as the criterion, and is warming up to 250 DEG C after adding, and keeps constant temperature in course of reaction.Every
10min sampling and measuring infrared spectrum, 1650cm-1Occur that acrylic double bond peak to double bond peak increases
To no longer changing, observing response situation, arrive viscosity very big after stopped reaction, cooling while hot
Pour out product, obtain yellow solid.
Embodiment 3:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:1 adds gallic acid, pyromellitic dianhydride, and accounts for the sulfur of reactant 5wt%
Acid, with acetone as reaction dissolvent, is heated to 60 DEG C of condensing refluxes.Every 30min sampling is passed through
Infrared analysis pyromellitic dianhydride esterification yield.Treat that anhydride is at 1847cm-1The infrared peak at place reduces
To no longer changing, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer change, show fully
After reaction, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.25g sulphuric acid, start stirring after being heated to fusing, when system temperature rises to 200 DEG C,
Dropping 0.5g methacrylate (containing 0.05g hydroquinone), rate of addition is with temperature
Inconspicuous decline is as the criterion, and is warming up to 210 DEG C after adding, and keeps constant temperature in course of reaction.Every
10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond peak occurs extremely
Double bond peak increases to no longer change, observing response situation, arrives the very big rear stopped reaction of viscosity,
Cooling also pours out product while hot, obtains yellow solid.
Embodiment 4:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:3 adds gallic acid, pyromellitic dianhydride, and accounts for the right of reactant 2wt%
Toluenesulfonic acid, with acetone as reaction dissolvent, is heated to 60 DEG C of condensing refluxes.Every 30min takes
Sample passes through infrared analysis pyromellitic dianhydride esterification yield.Treat that anhydride is at 1847cm-1That locates is infrared
Peak is decreased to no longer change, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer change, table
After bright abundant reaction, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.15g p-methyl benzenesulfonic acid, start stirring, treat that system temperature rises to after being heated to fusing
When 200 DEG C, dropping 1g methacrylate (containing 0.05g hydroquinone), dropping speed
Degree is as the criterion with the inconspicuous decline of temperature, is warming up to 200 DEG C after adding, and keeps perseverance in course of reaction
Temperature.Every 10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic acid occurs
Double bond peak to double bond peak increases to no longer change, observing response situation, stops after arrival viscosity is very big
Only reaction, cooling is also poured out product while hot, is obtained yellow solid.
Embodiment 5:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:2 addition sucrose, pyromellitic dianhydride, and account for the oxalic acid of reactant 3wt%,
With acetone as reaction dissolvent, it is heated to 60 DEG C of condensing refluxes.Every 30min samples by infrared
Analyze pyromellitic dianhydride esterification yield.Treat that anhydride is at 1847cm-1The infrared peak at place is decreased to not
Change again, simultaneously 3600cm-1Hydroxyl peak be also decreased to no longer change, show fully to react
After, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.05g oxalic acid, start stirring after being heated to fusing, when system temperature rises to 200 DEG C,
Dropping 1.5g methacrylate (containing 0.05g hydroquinone), rate of addition is with temperature
Inconspicuous decline is as the criterion, and is warming up to 225 DEG C after adding, and keeps constant temperature in course of reaction.Every
10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond peak occurs extremely
Double bond peak increases to no longer change, observing response situation, arrives the very big rear stopped reaction of viscosity,
Cooling also pours out product while hot, obtains yellow solid.
Embodiment 6:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:1 adds sucrose, pyromellitic dianhydride, and accounts for the borontrifluoride of reactant 0.5wt%
Boron, with acetone as reaction dissolvent, is heated to 60 DEG C of condensing refluxes.Every 30min sampling is passed through
Infrared analysis pyromellitic dianhydride esterification yield.Treat that anhydride is at 1847cm-1The infrared peak at place reduces
To no longer changing, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer change, show fully
After reaction, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.1g boron trifluoride, start stirring, treat that system temperature rises to 200 DEG C after being heated to fusing
Time, dropping 0.5g methacrylate (containing 0.05g hydroquinone), rate of addition with
The inconspicuous decline of temperature is as the criterion, and is warming up to 220 DEG C after adding, and keeps constant temperature in course of reaction.
Every 10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond occurs
Peak to double bond peak increases to no longer change, observing response situation, arrives the very big rear stopping of viscosity anti-
Should, cooling also pours out product while hot, obtains yellow solid.
Embodiment 7:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:3 adds cyclodextrin, phenylsuccinic acid acid anhydride, and accounts for the anhydrous of reactant 5wt%
Aluminum chloride, with acetone as reaction dissolvent, is heated to 60 DEG C of condensing refluxes.Every 30min sampling
By infrared analysis phenylsuccinic acid acid anhydride esterification yield.Treat that anhydride is at 1847cm-1The infrared peak at place
It is decreased to no longer change, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer change, show
Fully after reaction, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.025g anhydrous Aluminum chloride, start stirring, treat that system temperature rises to after being heated to fusing
When 200 DEG C, dropping 1g methacrylate (containing 0.05g hydroquinone), dropping speed
Degree is as the criterion with the inconspicuous decline of temperature, is warming up to 220 DEG C after adding, and keeps perseverance in course of reaction
Temperature.Every 10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic acid occurs
Double bond peak to double bond peak increases to no longer change, observing response situation, stops after arrival viscosity is very big
Only reaction, cooling is also poured out product while hot, is obtained yellow solid.
Embodiment 8:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:1 adds cyclodextrin, phenylsuccinic acid acid anhydride, and accounts for the chlorination of reactant 1wt%
Zinc, with acetone as reaction dissolvent, is heated to 60 DEG C of condensing refluxes.Every 30min sampling is passed through
Infrared analysis phenylsuccinic acid acid anhydride esterification yield.Treat that anhydride is at 1847cm-1The infrared peak at place reduces
To no longer changing, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer change, show fully
After reaction, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.075g zinc chloride, start stirring, treat that system temperature rises to 200 DEG C after being heated to fusing
Time, dropping 1.5g methacrylate (containing 0.05g hydroquinone), rate of addition with
The inconspicuous decline of temperature is as the criterion, and is warming up to 220 DEG C after adding, and keeps constant temperature in course of reaction.
Every 10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond occurs
Peak to double bond peak increases to no longer change, observing response situation, arrives the very big rear stopping of viscosity anti-
Should, cooling also pours out product while hot, obtains yellow solid.
Embodiment 9:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:1 addition cyclodextrin, phenylsuccinic acid acid anhydride, and account for the hydrochloric acid of reactant 5wt%,
With acetone as reaction dissolvent, it is heated to 60 DEG C of condensing refluxes.Every 30min samples by infrared
Analyze phenylsuccinic acid acid anhydride esterification yield.Treat that anhydride is at 1847cm-1The infrared peak at place is decreased to not
Change again, simultaneously 3600cm-1Hydroxyl peak be also decreased to no longer change, show fully to react
After, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.075g hydrochloric acid, start stirring after being heated to fusing, when system temperature rises to 200 DEG C,
Dropping 1.5g methacrylate (containing 0.05g hydroquinone), rate of addition is with temperature
Inconspicuous decline is as the criterion, and is warming up to 220 DEG C after adding, and keeps constant temperature in course of reaction.Often
Every 10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond peak occurs
Increase to no longer change to double bond peak, observing response situation, arrive the very big rear stopped reaction of viscosity,
Cooling also pours out product while hot, obtains yellow solid.
Embodiment 10:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:1 add glucose, 4, the double phthalic anhydride of 4'-oxygen, and account for reactant 4wt%
Sulphuric acid, with acetone as reaction dissolvent, be heated to 60 DEG C of condensing refluxes.Every 30min sampling
By the double phthalic anhydride esterification rate of infrared analysis 4,4'-oxygen.Treat that anhydride is at 1847cm-1Place
Infrared peak be decreased to no longer change, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer become
Changing, after showing fully to react, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.075g hydrochloric acid, start stirring after being heated to fusing, when system temperature rises to 200 DEG C,
Dropping 1.5g methacrylate (containing 0.05g hydroquinone), rate of addition is with temperature
Inconspicuous decline is as the criterion, and is warming up to 220 DEG C after adding, and keeps constant temperature in course of reaction.Every
10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond peak occurs extremely
Double bond peak increases to no longer change, observing response situation, arrives the very big rear stopped reaction of viscosity,
Cooling also pours out product while hot, obtains yellow solid.
Embodiment 11:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:1 add glucose, 4, the double phthalic anhydride of 4'-oxygen, and account for reactant 1.5wt%
Zinc chloride, with acetone as reaction dissolvent, be heated to 60 DEG C of condensing refluxes.Every 30min takes
Sample is by the double phthalic anhydride esterification rate of infrared analysis 4,4'-oxygen.Treat that anhydride is at 1847cm-1
The infrared peak at place is decreased to no longer change, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer
Change, after showing fully to react, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.075g anhydrous Aluminum chloride, start stirring, treat that system temperature rises to after being heated to fusing
When 200 DEG C, dropping 1.5g hydroxyethyl acrylate (containing 0.05g hydroquinone), rate of addition with
The inconspicuous decline of temperature is as the criterion, and is warming up to 220 DEG C after adding, and keeps constant temperature in course of reaction.
Every 10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond occurs
Peak to double bond peak increases to no longer change, observing response situation, arrives the very big rear stopping of viscosity anti-
Should, cooling also pours out product while hot, obtains yellow solid.
Embodiment 12:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:1 add glucose, 4, the double phthalic anhydride of 4'-oxygen, and account for reactant 5wt%
Zinc chloride, with acetone as reaction dissolvent, be heated to 60 DEG C of condensing refluxes.Every 30min takes
Sample is by the double phthalic anhydride esterification rate of infrared analysis 4,4'-oxygen.Treat that anhydride is at 1847cm-1
The infrared peak at place is decreased to no longer change, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer
Change, after showing fully to react, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.075g hydrochloric acid, start stirring after being heated to fusing, when system temperature rises to 200 DEG C,
Dropping 1.5g hydroxyethyl acrylate (containing 0.05g hydroquinone), rate of addition is failed to understand with temperature
Aobvious decline is as the criterion, and is warming up to 220 DEG C after adding, and keeps constant temperature in course of reaction.Every 10min
Sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond peak occurs to double bond peak
Increasing to no longer change, observing response situation, arrive the very big rear stopped reaction of viscosity, cooling is also
Pour out product while hot, obtain yellow solid.
Embodiment 13:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:1 add glucose, trimellitic anhydride, and account for reactant 5wt% to toluene
Sulfonic acid, with acetone as reaction dissolvent, is heated to 60 DEG C of condensing refluxes.Every 30min sampling is logical
Cross infrared analysis trimellitic anhydride esterification yield.Treat that anhydride is at 1847cm-1The infrared peak at place reduces
To no longer changing, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer change, show fully
After reaction, decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.075g boron trifluoride, start stirring, treat that system temperature rises to 200 DEG C after being heated to fusing
Time, dropping 1.5g hydroxyethyl acrylate (containing 0.05g hydroquinone), rate of addition is with temperature
Inconspicuous decline is as the criterion, and is warming up to 210 DEG C after adding, and keeps constant temperature in course of reaction.Every
10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond peak occurs extremely
Double bond peak increases to no longer change, observing response situation, arrives the very big rear stopped reaction of viscosity,
Cooling also pours out product while hot, obtains yellow solid.
Embodiment 14:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:1 addition glucose, trimellitic anhydride, and account for the oxalic acid of reactant 5wt%,
With acetone as reaction dissolvent, it is heated to 60 DEG C of condensing refluxes.Every 30min samples by infrared
Analyze trimellitic anhydride esterification yield.Treat that anhydride is at 1847cm-1The infrared peak at place is decreased to no longer
Change, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer change, after showing fully to react,
Decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.075g anhydrous Aluminum chloride, start stirring, treat that system temperature rises to after being heated to fusing
When 200 DEG C, dropping 1.5g hydroxyethyl acrylate (containing 0.05g hydroquinone), rate of addition with
The inconspicuous decline of temperature is as the criterion, and is warming up to 220 DEG C after adding, and keeps constant temperature in course of reaction.
Every 10min sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond occurs
Peak to double bond peak increases to no longer change, observing response situation, arrives the very big rear stopping of viscosity anti-
Should, cooling also pours out product while hot, obtains yellow solid.
Embodiment 15:
(1) in the 250mL four-hole boiling flask being furnished with agitating device, thermometer, condensing tube by
Mol ratio 1:1 addition glucose, trimellitic anhydride, and account for the zinc chloride of reactant 2wt%,
With acetone as reaction dissolvent, it is heated to 60 DEG C of condensing refluxes.Every 30min samples by infrared
Analyze trimellitic anhydride esterification yield.Treat that anhydride is at 1847cm-1The infrared peak at place is decreased to no longer
Change, 3600cm simultaneously-1Hydroxyl peak be also decreased to no longer change, after showing fully to react,
Decompression is distilled off solvent acetone, obtains pressed powder product.
(2) in equipped with the 250mL four-hole boiling flask of water knockout drum, add the product of 5g step (1)
Thing and 0.075g hydrochloric acid, start stirring after being heated to fusing, when system temperature rises to 200 DEG C,
Dropping 1.5g hydroxyethyl acrylate (containing 0.05g hydroquinone), rate of addition is failed to understand with temperature
Aobvious decline is as the criterion, and is warming up to 250 DEG C after adding, and keeps constant temperature in course of reaction.Every 10min
Sampling and measuring reactant mixture infrared spectrum, 1650cm-1Acrylic double bond peak occurs to double bond peak
Increasing to no longer change, observing response situation, arrive the very big rear stopped reaction of viscosity, cooling is also
Pour out product while hot, obtain yellow solid.
Application Example
Embodiment 16
Resin 70 mass parts that embodiment 1 is synthesized, diluent methyl methacrylate 30 matter
Amount part, light trigger 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl-1-acetone about 1 mass
Part, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone about 1.5 mass parts, 2,4,6-
Trimethylbenzoy-dipheny phosphine oxide about 1.5 mass parts, organic pigment C.I. indigo plant 60 about 1
The mixing of mass parts, wetting agent OT75 about 1 mass parts is put in container, many in SFJ-400 type
Pre-dispersed with carrying out on machine, pre-dispersed mixing 60min under conditions of rotating speed 1500rpm.Take
5ml mixture film forming on sol evenning machine, sol evenning machine rotating speed is 1000rpm, and the time is 15s.
The sheet glass of film forming is put into baking oven front baking 10min of 65 DEG C, is then exposed, exposure
Amount 2000mJ/cm2, develop in the potassium hydroxide solution of 1% concentration, 90 DEG C of after bake subsequently
1h, obtains light resistance coating 1.
Embodiment 17
With reference to embodiment 16, with the tree of resin replacement embodiment 1 synthesis of embodiment 5 synthesis
Fat, and amount of resin 60 mass parts, diluent 40 mass parts, other condition is constant, obtains light
Resistance coating 2.
Embodiment 18
With reference to embodiment 16, with the tree of resin replacement embodiment 1 synthesis of embodiment 9 synthesis
Fat, and replace organic pigment C.I. indigo plant 60 with organic pigment C.I. red 3, other condition is constant,
Obtain light resistance coating 3.
Embodiment 19
With reference to embodiment 16, with the tree of resin replacement embodiment 1 synthesis of embodiment 13 synthesis
Fat, and replace organic pigment C.I. indigo plant 60 with organic pigment C.I. black 11, other condition is constant,
Obtain light resistance coating 4.
Performance characterization
The light resistance coating 1-4 preparing above-described embodiment 16-19 carries out performance characterization, including table
Surface hardness, resistance to ag(e)ing, thermostability and endurance.Concrete detection method and step are as follows:
(1) case hardness measures: with reference to the detection method of standard GB/T/T 6739-1996
Carrying out test grading, grading number is the highest, represents that performance is the best.
(2) ageing-resistant performance measures and evaluation methodology: chromatic photoresist coating be positioned over
ATLAS-UV 2000 ageing device Continuous irradiation 200 hours, then by light resistance coating with desk-top
Aberration spectrophotometer Datacolor 600 tests the aberration (Δ E) after light resistance coating pre-irradiation,
Δ E value is the least, represents that light resistance coating resistance to ag(e)ing is the best.
(3) Heat-tolerance Determination and evaluation methodology: chromatic photoresist coating TGA-Q500 is surveyed
Heat decomposition temperature (the T of examination light resistance coatingd), TdIt is worth the biggest, represents that photoresistance coating heat resistance is more
Good.
(4) chemical resistance measures: chromatic photoresist coating is put into the vacuum drying oven of 60 DEG C
Middle baking 8 hours, takes out and light resistance coating is fully immersed in analytically pure acetone soln 30
Minute, then it is placed on air dry oven 40 DEG C and is dried 1 hour, observing light resistance coating has
Without wrinkling, foaming, variable color and eclipsed phenomenon.
Characterization result is as shown in the table.
As can be seen from the above table, the colors that the polyfunctionality light-cured resin of the present invention prepares are utilized
Light resistance coating has the highest hardness, and Δ E is little for aberration.Heat decomposition temperature (the T of each coatingd)
All more than 400 DEG C, fine heat-resisting performance.Analytically pure acetone soln soaks 30 minutes
And dried, light resistance coating, without wrinkling, foaming, variable color and eclipsed phenomenon, shows well
Chemical resistance.
To sum up, the polyfunctionality light-cured resin of the present invention can be used for preparing chromatic photoresist, prepares
Product hardness high, and there is thermostability, resistance to ag(e)ing and the resistance to chemical corrosion of excellence,
Have a extensive future.
Claims (9)
1. it is used for a preparation method for the polyfunctionality light-cured resin of chromatic photoresist, including
The following step:
(1) natural polyols is mixed with anhydride, under catalyst action in organic solvent
Carry out esterification, obtain intermediate product；
Described natural polyols is selected from gallic acid, sucrose, cyclodextrin or glucose, described acid
Acid anhydride is selected from pyromellitic dianhydride, trimellitic anhydride, the double phthalic anhydride of 4,4'-oxygen, adjacent benzene two
Formic anhydride or phenylsuccinic acid acid anhydride；
(2) intermediate product mixes with (methyl) acrylic acid hydroxy alkyl ester, in catalyst and resistance
Carry out esterification under poly-agent existence condition, obtain product.
Preparation method the most according to claim 1, it is characterised in that: in step (1),
Natural polyols is 1:1-5 with the mol ratio of anhydride.
Preparation method the most according to claim 1 and 2, it is characterised in that: step (1)
In, catalyst is hydrochloric acid, sulphuric acid, p-methyl benzenesulfonic acid, oxalic acid, boron trifluoride, anhydrous chlorination
One or more combination in aluminum or zinc chloride.
Preparation method the most according to claim 1, it is characterised in that: in step (2),
The 5-30wt% that amount is intermediate product of (methyl) acrylic acid hydroxy alkyl ester.
5. according to the preparation method described in claim 1 or 4, it is characterised in that: step (2)
In, catalyst is hydrochloric acid, sulphuric acid, p-methyl benzenesulfonic acid, oxalic acid, boron trifluoride, anhydrous chlorination
One or more combination in aluminum or zinc chloride.
6. according to the preparation method described in claim 1 or 4, it is characterised in that: step (2)
In, polymerization inhibitor be hydroquinone, 1,4-benzoquinone, phenothiazine, beta-phenyl naphthylamines, to tert-butyl o
One or more combination in Benzodiazepines.
7. according to the preparation method described in claim 1 or 4, it is characterised in that: step (2)
In, reaction temperature is 200-250 DEG C.
8., for a polyfunctionality light-cured resin for chromatic photoresist, it is by claim 1-7
According to any one of preparation method be prepared from.
9. the polyfunctionality light-cured resin described in claim 8 is in preparing chromatic photoresist
Application.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113150188A (en) * | 2020-11-23 | 2021-07-23 | 濮阳展辰新材料有限公司 | Preparation method of cyclodextrin-based light-cured resin and application of cyclodextrin-based light-cured resin in coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824209A (en) * | 2010-04-09 | 2010-09-08 | 湖南大学 | Preparation method of polyester acrylate hybrid aqueous dispersion |
| CN102863592A (en) * | 2012-10-18 | 2013-01-09 | 常州华日新材有限公司 | Preparation method for transparent thixotropic unsaturated polyester resin |
| CN105061739A (en) * | 2015-09-08 | 2015-11-18 | 常州华科聚合物股份有限公司 | Paint resin for cans/tins and preparation method thereof, and paint composition for cans/tins |
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2016
- 2016-05-17 CN CN201610327811.1A patent/CN105968334B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824209A (en) * | 2010-04-09 | 2010-09-08 | 湖南大学 | Preparation method of polyester acrylate hybrid aqueous dispersion |
| CN102863592A (en) * | 2012-10-18 | 2013-01-09 | 常州华日新材有限公司 | Preparation method for transparent thixotropic unsaturated polyester resin |
| CN105061739A (en) * | 2015-09-08 | 2015-11-18 | 常州华科聚合物股份有限公司 | Paint resin for cans/tins and preparation method thereof, and paint composition for cans/tins |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150188A (en) * | 2020-11-23 | 2021-07-23 | 濮阳展辰新材料有限公司 | Preparation method of cyclodextrin-based light-cured resin and application of cyclodextrin-based light-cured resin in coating |
| CN113150188B (en) * | 2020-11-23 | 2022-05-31 | 濮阳展辰新材料有限公司 | Preparation method of cyclodextrin-based light-cured resin and application of cyclodextrin-based light-cured resin in coating |
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