CN1028433C - Optical solidification compound and preparation method and application thereof - Google Patents
Optical solidification compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN1028433C CN1028433C CN 89100518 CN89100518A CN1028433C CN 1028433 C CN1028433 C CN 1028433C CN 89100518 CN89100518 CN 89100518 CN 89100518 A CN89100518 A CN 89100518A CN 1028433 C CN1028433 C CN 1028433C
- Authority
- CN
- China
- Prior art keywords
- rosin
- acid
- methyl
- composition
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a light curing composition, a preparation method of main components of the light curing composition and the preparation and the application of the composition. Combined rosin and amine modification epoxy (methyl radical) acrylic ester or rosin modification alcohol acid (methyl radical) acrylic ester prepolymers are used as the main components of the composition; the composition can be stored for long time and has high performance; the polymer thin film of the composition has the advantages of brightness, firmness, impact resistance, friction resistance and corrosion resistance, and can be used as paper, wood, leather, fiber, metal, plastics, ceramics, stone material and surface protective layers of the products. The present invention has the advantage of low manufacture cost, and is a path for developing and utilizing rosin and turpentine.
Description
The present invention relates to Photocurable composition and the preparation method of main component and preparation of composition and uses thereof,
Epoxy acrylate is the important component of composite reinforcing materials such as Photocurable composition (as coating) and glass reinforced plastic, and this class ester is normally by Resins, epoxy and vinylformic acid, and under quaternary ammonium salt or triethylamine catalysis, reaction makes under 100 ℃ or higher temperature.Because the temperature height, product is easy to polymerization, if add more stopper, then can influence product in using afterwards polymerization and the color and luster of its polymkeric substance that forms.For this reason, seek catalyzer efficiently, reduce temperature of reaction and be one of problem that synthetic this resinoid need solve.In addition, require it to have quick light-cured performance as light-cured component, this not only is related to its service efficiency and purposes, also can influence the quality of cured article (for example film), because have only fast setting just can avoid the inhibition of oxygen in the air, make polymkeric substance (as film) light hard.Usually adopt the way that adds relatively large Photoepolymerizationinitiater initiater to make it to solidify as early as possible, its consumption can be up to percentum of whole system weight, but the softening agent of the become polymkeric substance that these micromolecular initiators have reduces the mechanical property of polymkeric substance, and what have can also ooze out and contaminate environment.Have been found that now tertiary amine particularly trolamine be the important promotor of Photoepolymerizationinitiater initiater, in the presence of it, in air, also can accelerate laser curing velocity, and itself odorless, tasteless (Jiang Shuojian, Li Wen
In the coatings industry submission; Roffey, C.G.photopolymerization of Surface Coatings, Wiley Interacience Publication 1982) but its polarity is bigger, difficult with treat that some components in the light solids mix, thereby influenced its application.In addition, the polarity of epoxy acrylate is also bigger, with some non-polar monomers and non-polar solvent mix difficult, so by the combined stream levelling of forming poor, and the brightness behind the photocuring is also not ideal enough.
The present invention is directed to the problems referred to above a solution is provided, but its objective is by a series of steps that address the above problem and obtain standing storage, the prepolymer of the alkyd acrylic or methacrylic acid esters of the Resins, epoxy acrylic or methacrylic acid esters of well behaved rosin based and amine modification or rosin based modification, be mixed with the composition of photocuring rapidly and this based composition is widely used by such prepolymer, seek out a feasible approach for the natural resource rosin and the turps of development and use China's abundant simultaneously.
United States Patent (USP), 4253,918 disclose the preparation method of the Resins, epoxy acrylic or methacrylic acid esters of using the amine modification and the photopolymerizable composition of forming with such ester, but often need to add lower boiling solvent in order to make it good levelling property, but easily pollute.The present invention adopts the alkyd acrylate of the epoxy acrylic of new rosin based and amine modification or methacrylic ester or rosin based modification or the methacrylate prepolymers main ingredient as composition, owing in prepolymer, introduced the oil soluble that the rosin based ester group has increased described prepolymer, improved the luminance brightness that is mixed with the levelling property and the photopolymer of composition by it, and the consumption of rosin based can be up to 50% of epoxy group(ing) mole number, 10-35% preferably, thereby can reduce the consumption of acrylic or methacrylic acid, Synolac is cheap simultaneously, thereby can reduce the cost of composition significantly, make abundant natural resource rosin obtain better application in addition.When the system prepolymer, adopt the used reactive thinner of compositions formulated to make solvent, not only help reaction but also do not need except that desolvating.Because it is unclean that steaming desolventizes very difficult steaming again, also be easy to cause resin crosslinks that product is scrapped.Photocurable composition of the present invention mainly is made up of above-mentioned prepolymer and reactive thinner and Photoepolymerizationinitiater initiater.Said composition can be used as the protective layer of variety carrier.
Used Resins, epoxy can be the ethers of binary or polyphenol or alcohol and the formation of dehydration glycerine among the present invention; The ester class that binary or polycarboxylic acid and dehydration glycerine form, for example dihydroxyphenyl propane, bisphenol S, butyleneglycol, trihydroxy-propane, tetramethylolmethane etc. and the special ester class (B) that forms with two dehydration glycerine of ethers (A), phthalic acid, hydrogenation of benzene dioctyl phthalate, kautschin and the maleic anhydride adduct of the formation of two dehydration glycerine
The amination of above epoxy resin can be used for example for example diethanolamine, diisopropanolamine (DIPA) of thanomin, Yi Bingchunan, secondary amine of ammonia, primary amine, but better with secondary amine such as diethanolamine.The amination amount can reach 50% of epoxy group(ing) mole number, is 5-30% preferably, is preferably lower than 15%.
Rosin based can be selected natural rosin or hydrogenation natural rosin, nilox resin, dimerization or poly rosin or accurately machined above-mentioned rosin for use, and its esterification amount can be up to 50% of epoxy group(ing) mole number, is preferably to be lower than 40%, is preferably in 10-35%.
Acrylic acid or the like can be used vinylformic acid, methacrylic acid, and the esterification amount should be greater than 50% of epoxy group(ing) mole number.And the mole number summation of acrylic acid or the like, rosin based and amine should not surpass the epoxy group(ing) mole number, and should near or be lower than its mole number slightly.The ester of handy respective acids is made solvent when carrying out esterification with acrylic acid or the like.
The catalyzer that the epoxy reaction of rosin based and acrylic acid or the like and described resin prepares prepolymer is the mixture of tertiary amine and alkyl thioether, the tertiary amine that tertiary amine is produced in the time of can being amination Resins, epoxy, the optional usefulness of alkyl thioether is sulfo-glycol ether or sulfo-di-isopropylene glycol for example, and its consumption is the 0.01-3% of Resins, epoxy.When reacting with rosin based, temperature is between 60-100 ℃, when reacting with vinylformic acid, temperature is between 40-80 ℃ and need add a small amount of stopper, for example Resorcinol, hydroquinone monomethyl ether, its consumption is the 0.05-0.2% of acrylic acid or the like weight, and the degree of esterification of the two all can learn that acid number should be reduced between the 0-10 by measuring acid number.More than reaction need be carried out 12-18 hour altogether.
The alkyd acrylate of the rosin based modification among the present invention or its methacrylic ester are at alkyd (methyl) acrylate (United States Patent (USP) 4,206,025) introduce the rosin based ester group in, improved levelling property, luminance brightness and the cohesiveness of polymkeric substance (as film), its preparation approach is as follows
N is greater than m, and L and k, n are greater than 2.
ACOOH represents rosin based.R(OH)
nRepresent polyvalent alcohol.HOOC-R '-COOH represents di-carboxylic acid.Rosin based herein as previously mentioned.Polyvalent alcohol wherein comprises: tetramethylolmethane, dipentaerythritol, TriMethylolPropane(TMP), trolamine etc.Di-carboxylic acid comprises: hexanodioic acid, sebacic acid, kautschin maleic anhydride affixture, hydrogenation kautschin maleic anhydride affixture, Tetra hydro Phthalic anhydride, m-phthalic acid etc.
(1) in preparation, make polyvalent alcohol and rosin based earlier under nitrogen protection; in the presence of acid, alkali or neutral catalyst, in 200-300 ℃ of reacting by heating and steam formed water, the degree that reacts completely can be learnt by the mensuration acid number; the general requirement acid number is reduced to below 10, gets product (C).Described catalyzer serves as that better consumption is the 0.05-0.15% of reactant weight with Quilonum Retard, phosphorous acid.Polyvalent alcohol and rosin based mol ratio 1: 1-2, reaction times 5-8 hour.
(2) will more than after the product that obtains mixes with binary carboxylic carboxylic acid with 2: 1 mol ratio, under the nitrogen protection, in 240-290 ℃ of reacting by heating and steam water, reduce to 10 following termination reactions to acid number, must product (D).Reaction times 2-3 hour.
(1) and the product in (2) all can carry out transesterify with (methyl) methyl acrylate, be reflected under the magnesium alkoxide catalysis and carry out, and steam the methyl alcohol of generation at any time.Catalyst consumption is the 0.05-1% of reactant weight.The ratio of (methyl) methyl acrylate and the mole number of Synolac can be at 6-8: 1.Form alkyd (methyl) acrylate of corresponding rosin based modification, it is acrylate-based to contain more than two (methyl) in this ester molecule, promptly can be used as the main ingredient that prepolymer is described composition.Temperature of reaction 110-130 ℃, time 0.5-2 hour.
Photocurable composition mainly is made up of above-mentioned prepolymer, reactive thinner and Photoepolymerizationinitiater initiater.Reactive thinner is in order to make prepolymer reach suitable coating viscosity and to become cured article (for example film) with prepolymer when the photocuring, having avoided with other solvents owing to volatilization causes environmental pollution.Reactive thinner can be selected the ester class of acrylic or methacrylic acid for use, oneself, hydroxyl second, hydroxypropyl, benzene oxygen ethyl, benzene first, iso-borneol, dicyclo amylene 2-ethoxyethyl acetate and vinylbenzene of their first, second, fourth, 2-ethyl for example, or two or more the mixture in them, the weight ratio of reactive thinner and prepolymer is 1-1.2: 1.In reactive thinner, can be equipped with an amount of linking agent, for example pentaerythritol triacrylate, trimethylolpropene acid esters, 1.3-propylene glycol diacrylate, butylene glycol diacrylate, Vinylstyrene etc., to change the performance of photocuring thing, for example anti-ethanol, consumption are the 0-30% of composition.For the prepolymer viscosity adjustment after will diluting is coated with to being more convenient for, can add some non-activated thinners, for example can select acetate ethanol, butylacetate, acetone, methylethylketone, pimelinketone for use, consumption can be the 0-30% of whole solution weight.
When in air, being cured with UV-irradiation, available Photoepolymerizationinitiater initiater comprises: benzophenone-trolamine system or alpha-substitution st-yrax ethers, α-phenmethyl benzoin methyl ether for example, consumption respectively is the 0.1-6% of whole polymerization composition, the big curing speed of consumption is correspondingly accelerated.The general photocuring time 1 second in 60 seconds, the concrete time is decided by the component, purity, fluorescent tube distance, voltage, fluorescent tube degree of aging, coat-thickness of composition etc.
Ultraviolet source is a high voltage mercury lamp, and the every cm long radiation flux of fluorescent tube is not less than 80 watts.About 10 centimetres of the distance of photocuring sample and fluorescent tube.The high-pressure mercury fluorescent tube is outer should refrigerating unit, for example the quartzy chuck of water cooling.In addition, hurt sb.'s feelings the device that the overall optical cure system need have shield cap and get rid of the ozone that is produced by action of ultraviolet light for fear of UV-light.
The present composition through aforesaid method preparation can adopt coating, spray, flood and other any composition can being attached on true qualities or painted paper, wood, leather, fiber, metal, plastics, pottery, glass, building stones etc. or their product surface, then the membranaceous protective layer of formation polymer thin, light, firm, prolonged, acid-and base-resisting and organic solvent through UV-irradiation and on each carrier surface as mentioned above.
The hardness of described polymeric film can be fixed with the QBY type oscillating rod type hardness of paint film instrumentation that Tianjin material-testing machine factory makes, and stiffness units is that the zero point of glass hard (HRC65 is several.
The shock resistance of polymer thin film can be measured with the Q153-3K1 type paint film impactor that Tianjin material-testing machine factory makes, and unit is kg-cm.
The sticking power of polymeric film can be measured with the QFZ II type Coating adhesion test instrument that Tianjin material-testing machine factory makes.Draw no any film with stylus and come off for excellent, the edge have slightly come off for the spiral pattern intersection good, that pin streaks come off in, the big area of film comes off for poor.
Appearance method is generally taked in the brightness of polymeric film, is marked with " good ", and generally the mirror surface luster instrument made from Tianjin instrument experiment factory of science equipment company is measured brightness more than 100.
The levelling degree take the range estimation, be marked with " good ", show that very fast levelling is as bright as a sixpence on the plank that for example is coated in alcohol acid primer.
There are point, wrinkle etc. also all to be as the criterion on the film with range estimation.
The reagent resistance energy of film, with water, 10% sodium hydroxide, 10% yellow soda ash, 10% sulfuric acid and dehydrated alcohol are tested as reagent.Each three of every kind of reagent are covered with cover on film, leave standstill the variation of viewing film after 24 hours.No trace is marked (-) after wiping liquid, and expression is not corroded; Slightly turn white and be marked with (+) expression slight corrosion arranged; Film has to come off on a small quantity and is marked with (++) expression corrosion arranged; Having seriously comes off is marked with (+++).
In order to be illustrated more clearly in the present invention, enumerate the following example, these embodiment limit scope of the present invention.
Embodiment 1
Synthesizing of the epoxy acrylate of rosin based and amine modification:
(epoxy equivalent (weight) is 208 to add 25 gram dihydroxyphenyl propanes, two glycidyl ethers in 250 milliliters of there-necked flasks, contain 0.12 mole of epoxy group(ing)), (acid equivalent is 332 to rosin 8.3 grams, contain 0.025 mole of carboxyl), make it dissolving with heating in 85 ℃ of water-baths and stirring, react after one hour, slowly drip diethanolamine 0.5 gram (0.0048 mole) by dropper, react adding sulfo-glycol ether 0.25 gram after a hour, record acid number this moment is 32.6.Continue reaction 2 hours, surveying acid number is 1.3.
Bath temperature is reduced to 60 ℃, add isobornyl acrylate 13 grams (wherein containing hydroquinone monomethyl ether's 0.02 gram), stir evenly 5.4 gram (0.075 mole includes 0.1% hydroquinone monomethyl ether) of back dropwise addition of acrylic acid.Dripped in 2 hours.Continue reaction 13 hours, record acid number about 20.Drip diethanolamine 0.5 gram (0.0048 mole) with dropper, continue reaction 2 hours, record acid number less than 10.
Use isobornyl acrylate (the containing 0.1% hydroquinone monomethyl ether) dilution of aequum while hot, stir evenly the back and in cold water, cool off, product is poured in the brown bottle preserved then.Epoxy group(ing) is 7.5/12 by the ratio of acroleic acid esterification in this resin, and epoxy group(ing) is 2.5/12 by the ratio of rosin esterification; By aminating ratio is 0.96/12, and esterified altogether and amination ratio is 11/12.
With change rosin and staybelite (acid equivalent is 332) amount with quadrat method, a series of rosin based and amine modified epoxy acrylic ester have been synthesized.Gained the results are shown in Table one.
Table one different amount rosin based synthetic rosin based and amine modified epoxy acrylic ester
Dihydroxyphenyl propane two glycidyl ethers were all 25 grams (0.12 mole) during each was filled a prescription in the table
The diethanolamine consumption is 1 gram.
Rosin represents that with A staybelite is represented with HA.
The gained resin is respectively with I
A, I
HAExpression, I is a formula I, and A is Abietyl modified, and HA is a modified by hydrogenated rosin.(table 1 is seen the literary composition back)
Embodiment 2
Synthesizing of hydroxyl rosin pentaerythritol ester class ester:
In 100 milliliters of there-necked flasks, add rosin based 50 grams (0.16 mole), phosphorous acid (H
3PO
3) 0.103 gram (rosin based weight 0.2%), load onto agitator, thermometer connects prolong to collect the water that reaction steams.Under the nitrogen protection, the salt bath internal heating dissolves, and controlled temperature slowly adds tetramethylolmethane 22.3 grams (0.16 mole) at 200 ℃; and stir immediately, be warming up to 270 ℃ then, reacted 6 hours, take advantage of heat that product is poured in the mortar; product is the yellow transparent solid, grinds to store, and acid number is 8.9.
Phosphorous acid also can be changed to Quilonum Retard, and consumption is 0.2% of a rosin based weight, and rosin based is rosin, staybelite or nilox resin.The mol ratio of tetramethylolmethane and rosin based can be between 1-2.
Embodiment 3
Synthesizing of hydroxyl tetramethylolmethane di-carboxylic acid rosin based ester:
1. single stage method: in 100 milliliters of there-necked flasks, add staybelite 18.2 grams (0.06 mole), tetramethylolmethane 8.2 gram (0.06 mole), hexanodioic acid 4.4 grams (0.03 mole) and Quilonum Retard 0.0308 gram (account for total reactant heavy 0.1%) are loaded onto agitator, thermometer, are connected prolong and collect the water that reaction steams.Under nitrogen protection, heat and be controlled at 270 ℃, react 7 hours, take advantage of heat to pour mortar into, grind storage.Recording acid number is 1.81, and product is brown.
Synthesized following hydroxyl tetramethylolmethane di-carboxylic acid rosin based ester by similar approach, as following table two.(table two is seen the literary composition back)
2. two step method: the hydroxyl rosin pentaerythritol ester class ester of embodiment 2 gained is reacted with di-carboxylic acid again.
In 100 milliliters of there-necked flasks, add the mixture of tetramethylolmethane-hydrogenated wood rosin glycerol ester 27.9 grams (0.066 mole) and hexylene glycol 4.8 grams (0.033 mole), load onto agitator, thermometer, connect prolong to collect the water that reaction steams.Under the nitrogen protection, heat fused is warming up to 270 ℃ gradually, reacts 3 hours.Take advantage of heat that product is poured in the mortar, grind storage.Acid number is 7.8, yellow.
Get with two hydrogenated wood rosin glycerol esters 46.5 grams (0.065 mole) of tetramethylolmethane and hexanodioic acid 4.8 gram (0.033 mole) mixture reactions equally and sourly plant 8.0, the xanchromatic product.
Embodiment 4
Synthesizing of alkyd methacrylic ester:
1. magnesium methylate crystalline preparation: 100 milliliters of absolute anhydrous methanols are placed 250 milliliters of round-bottomed flasks of exsiccant, load onto the reflux condensing tube that has drying tube, add 1.6 gram magnesium rods and a small amount of iodine, after treating that magnesium rod has reacted, place colourless needle crystal, suction filtration places exsiccator to drain rapidly, gets the magnesium methylate crystal.Be stored in the exsiccator.
2. ester-interchange method synthol acid methyl acrylate: adorn a fractional column on 100 milliliters of there-necked flasks, fully insulation adds thermometer at capital, connects high-efficiency condensation pipe and receptor, there-necked flask in addition two mouthfuls load onto agitator and thermometer.0.030 mole of tetramethylolmethane di-carboxylic acid rosin based ester (wherein the mol ratio of tetramethylolmethane, binary hydroxyl carboxylic, rosin based is 2: 1: 2) that the interior adding of bottle is hydroxyl or hydroxyl rosin pentaerythritol ester class ester (wherein the mol ratio of tetramethylolmethane, rosin based is 1: 1), 0.2 mole of methyl methacrylate, Resorcinol and magnesium methylate (account for respectively reaction-ure mixture 0.1%).Under fully stirring, in oil bath, be heated to 120 ℃, reacted 1 hour, collect 63-84 ℃ of fraction, claim its weight and survey its refractive index.Graph of a relation according to methyl methacrylate and methyl alcohol composition and refractive index calculates and steams quantity of methyl alcohol, and then calculates the esterified percentage of hydroxyl on the alkyd resin.Reach more than 60% at this condition esterification yield, promptly on average can have more than two on the molecule of tetramethylolmethane di-carboxylic acid rosin based ester methacrylate based, and each molecule of rosin pentaerythritol ester class ester on average can have two methacrylate based.(table three is seen the literary composition back)
Embodiment 5
With rosin based and amine modified epoxy acrylic ester basic recipe and film forming performance by the Photocurable composition of prepolymer:
With 50 parts of rosin based and amine modified epoxy acrylic esters, 40 parts of isobornyl acrylate, 10 parts of methyl methacrylates, 2 parts of benzophenone, 2 parts of trolamines, being mixed into transparent liquid, is to be coated with on the plank of priming paint, the iron plate of wiping zinc coating and the washed glass plate in colouring with alkyd respectively, the every approximately 1mg/cm of coat-thickness
2About, illumination curing, ultraviolet source is that the Beijing Electrooptic Source Inst produces long 12cm, 1000 watts mercury lamp, the logical distilled water of the quartzy chuck of fluorescent tube external application cools off, and electric fan is blown away ozone, and fluorescent tube is apart from 10cm, illumination 40 seconds.The plank of priming is in order to viewing film brightness, levelling property and outward appearance.Iron plate is in order to test anti-impact and sticking power.Sheet glass is in order to measure hardness.Gained the results are shown in Table four (table four is seen the literary composition back)
As bright as a sixpence from film light, good leveling property, acid-and base-resisting and the water, particularly modified by hydrogenated rosin of the visible rosin based of table four and the Photocurable composition formation of amine modified epoxy acrylic ester preparation.But not anti-dehydrated alcohol.
Embodiment 6
The photocuring time is to the influence of film performance:
Descend with the increase of rosin based content from the visible film hardness of table four, particularly Abietyl modified decline is more remarkable.This is because the increase of rosin based has reduced acrylate-based content in resin, thereby has reduced the polymerization velocity of resin, and rosin also has certain retardation, and it is more obvious that film hardness is descended.Prolong the photocuring time, can improve extent of polymerization, increase hardness, but anti-impact and sticking power also descend to some extent.As V
HABy the prescription of example 5, similarity condition, different photocuring time gained the results are shown in Table five.
The table five photocuring time is to the influence of paint film property
Photocuring time (second) hardness anti-impact sticking power
40 0.49＞50 is excellent
60 0.59 49 is excellent
90 0.65 45 is excellent
120 0.66 42 is excellent
150 0.68 37 is excellent
180 0.68 35 is good
Embodiment 7
The influence of linking agent in prescription:
From visible rosin based of table four and the amine modified epoxy acrylic ester not anti-dehydrated alcohol of film that institute's composition prepared forms when cross-linking agent-free exists.In composite formula, add suitable linking agent and can improve its anti-alcohol performance.For example:
II
HA50 parts, 40 parts of isobornyl acrylate, 10 parts of methyl methacrylates, 2 parts of benzophenone, 2 parts of trolamines, add respectively in addition 5 parts of pentaerythritol triacrylates, 10 parts, 20 parts with 30 parts.With example 6 conditions, photocuring 40 seconds.Get result such as table six.(table six is seen the literary composition back)
Can improve anti-dehydrated alcohol and hardness from the visible linking agent pentaerythritol triacrylate that adds of table six, but anti-impact and sticking power descend slightly.
Embodiment 8
The relation of point and solvent:
Point (goose pimples) to occur be the problem that causes owing to many-sided reason to paint film behind the photocuring, as the problem in dust, bottom thing, the coating, during compositions formulated because resin and solvent solubility parameters discomfort also can cause point.
For example use V
HA50 parts, 40 parts of isobornyl acrylate, 2 parts of benzophenone, 2 parts of trolamines add the non-proton reactive thinner of some opposed polarities more respectively, point just occurs if solvent polarity amount greatly is many again, as table seven.(table seven is seen the literary composition back)
I for example again
A50 parts, by last example prescription.Because I
AMiddle rosin amount is few, adds the little solvent of polarity and point then occurs.If as table eight (table eight is seen the literary composition back)
Embodiment 9
Reactive thinner forms the influence of wrinkle to film:
Can see that from table four working as the rosin content increase can make film wrinkle occur.This is because rosin has certain slow polymerization, causes polymerization slow, and inconsistent again in the table, and the top layer polymerization is fast, sharply shrinks, and causes the epidermis formation wrinkle that splits.Therefore suitably adding quick polymeric reactive thinner amount can alleviate this phenomenon or eliminate.
For example use V
A50 parts, 40 parts of isobornyl acrylate, 2 parts of benzophenone, 2 parts of trolamines add different polymerizations of measuring methyl methacrylate and the slower vinylbenzene of polymerization faster respectively, can produce the different film of wrinkle result, result such as table nine.(table nine is seen the literary composition back).
Embodiment 10
With rosin based acid modified alcoholic (methyl) acrylate is the basic recipe and the film performance of the Photocurable composition of prepolymer:
All be equipped with 2 parts of benzophenone, 3 parts of trolamines in 100 parts of prepolymer and the reactive thinners, be to be coated with on the plank of priming paint, the iron plate of wiping zinc coating and the washed glass plate in colouring with alkyd respectively, treat illumination curing (condition similar embodiment 5) behind the levelling slightly.Used prepolymer sees Table ten, and the gained test result sees Table 11.(table ten sees the literary composition back)
Table ten prepolymer numbering
1. tetramethylolmethane staybelite hexanodioic acid methacrylic ester
2. rosin pentaerythritol ester hexanodioic acid methacrylic ester
3. tetramethylolmethane staybelite phthalic acid methacrylic ester
4. tetramethylolmethane trolamine staybelite phthalic acid methacrylic ester
5. tetramethylolmethane staybelite methacrylic ester
The performance of the Photocurable composition of table ten different rosin based acid modified alcoholic methacrylic ester preparations:
The generated data of table tripentaerythritol hexanodioic acid staybelite methacrylic ester
Tetramethylolmethane hexanodioic acid hydrogenated wood rosin glycerol ester 29 gram (0.030 mole) hydroxyls
Instead (2: 1: 2 moles of synthetic ratios) (0.12 mole)
Answer methyl methacrylate 20 grams (0.20 mole)
Thing Resorcinol 0.050 gram (accounting for gross weight 0.1%)
Magnesium methylate 0.050 gram (accounting for gross weight 0.1%)
During the reaction of 120 ℃ of temperature of reaction 1 hour
63-84 ℃ of weight of overhead product boiling range 9 gram η
201.3905
Methanol content 27.3% is heavy by 2.458
Hydroxyl is by methacrylated rate 64% on the tetramethylolmethane hexanodioic acid hydrogenated wood rosin glycerol ester
There are methacrylate based 2.56 on the average per molecule Synolac
Get product 39.4 grams, brown, wherein contain methyl methacrylate 5.18 grams
The performance of the Photocurable composition of different rosin based of table four and amine-modified epoxy resin preparation
The resin I
HAII
HAIII
HAIV
HAV
HAI
AII
AIII
AIV
AV
A
Hardness 0.61 0.60 0.57 0.48 0.49 0.55 0.41 0.50 0.44 0.27
Anti-impact＞50＞50＞50 49 50＞50 47＞50＞50＞50
Sticking power is good good excellent excellent
Brightness is bright bright
Good leveling property is good carefully carefully
Point does not have
Wrinkle does not have and slightly has
Water----------
10%NaOH - - - - - - - - - -
10%Na
2CO
3- - - - - - - - - -
10%H
2SO
4- - - - - - - - - -
Dehydrated alcohol ++ ++ +++++++++++++ ++++++
Table six:
Cross-linked dosage (part) 05 10 20 30
Hardness 0.60 0.67 0.80 0.82 0.84
Anti-impact＞50 50 50 48 45
Sticking power is good good good
Brightness is bright bright
Good leveling property carefully
The electrodeless light utmost point of point is light gently
Wrinkle does not have
Water-----
10%NaOH - - - - -
10%H
2SO
4- - - - -
Dehydrated alcohol++---
Claims (7)
1, a kind of Photocurable composition, it is characterized in that, this based composition is mainly by through epoxy (methyl) acrylate of rosin based and amine modification or alkyd (methyl) acrylic ester prepolymer of rosin based modification, reactive thinner and Photoepolymerizationinitiater initiater are formed, wherein can also add non-activated thinner, linking agent, form described prepolymer rosin based, amine and (methyl) acrylate the mole number summation less than or approach the mole number of epoxy group(ing), wherein:
Described rosin based: be selected from natural rosin or hydrogenation natural rosin, nilox resin, dimerization colophonium or accurately machined above-mentioned rosin, the esterification amount is lower than 40% of epoxy group(ing) mole number;
Described amine: be selected from ammonia, primary amine, can select thanomin, Yi Bingchunan, secondary amine for use, can select diethanolamine or diisopropanolamine (DIPA) for use, the amination amount can reach the 5-50% that goes back oxygen base mole number;
The esterification amount of described (methyl) acrylate should be greater than 50% of epoxy group(ing) mole number, or has more than two (methyl) acrylate-based on per molecule alkyd (methyl) acrylate;
Described reactive thinner: the ester class that is selected from acrylic or methacrylic acid, comprise: the mixture of the base of methyl, ethyl, butyl, 2-ethyl-, hydroxyethyl, hydroxypropyl, phenoxy group, phenmethyl, different ice place base, dicyclo amylene oxygen ethyl ester, vinylbenzene or above-mentioned two kinds or more of compounds, the weight ratio of reactive thinner and prepolymer is 1-1.2: 1;
Non-activated thinner: be selected from following classes of compounds, hydro carbons: comprise cyclohexane, sherwood oil, the ester class: comprise ethyl acetate, ethyl ester, butyl ester, ketone: comprise methylethylketone, cyclohexanone, or their mixture, consumption is the 0-30% of composition weight;
Linking agent: be selected from pentaerythritol triacrylate, Viscoat 295 or Vinylstyrene, consumption is the 0-20% of composition weight;
Photoepolymerizationinitiater initiater: be selected from benzophenone-trolamine system, alpha-substitution st-yrax ethers: comprise the alpha-substitution benzoin ether, consumption is the 0.1-6% of polymerization composition weight.
2, according to the composition of claim 1, it is characterized in that, composition includes only described epoxy (methyl) acrylic ester prepolymer, reactive thinner and Photoepolymerizationinitiater initiater, reactive thinner is the mixture of isobornyl acrylate and methyl methacrylate, and the weight ratio of the two is: 4: 1-2: 1.
According to the composition of claim 1 or 2, it is characterized in that 3, the rosin based in the prepolymer is a staybelite, amine is a diethanolamine, and the weight ratio of active attenuant mixture is 4: 1, in composition, be added with the linking agent that accounts for composition weight 5-30%, can select pentaerythritol triacrylate for use.
According to the composition of claim 1 or 2, it is characterized in that 4, reactive thinner is an isobornyl acrylate, methyl methacrylate and vinylbenzene, three's weight ratio is followed successively by 8: (1-2): (1-3).
5, according to the composition of claim 1, it is characterized in that, described prepolymer is a kind of alkyd (methyl) esters of acrylic acid of rosin based modification, comprising selecting rosin pentaerythritol ester hexanodioic acid methacrylic ester, tetramethylolmethane staybelite hexanodioic acid methacrylic ester, tetramethylolmethane trolamine staybelite phthalic acid methacrylic ester or tetramethylolmethane staybelite methacrylic ester, reactive thinner is selected from isobornyl acrylate or methyl methacrylate.
6, the preparation method of Photocurable composition is characterized in that, described method comprises:
1) preparation of (methyl) acrylic ester prepolymer of rosin based modification, comprising: epoxy (methyl) the esters of acrylic acid prepolymer of rosin based and amine modification, the alkyd of rosin based modification (methyl) acrylic ester prepolymer;
(1) epoxy (methyl) acrylic ester prepolymer of rosin based and amine modification:
Make rosin based and amine in the presence of catalyzer, reacted 2-3 hour with Resins, epoxy in 60-100 ℃, when reducing to 0-10 Deng acid number, add an amount of esters of acrylic acid (stopper that contains the 0.01-0.2% of its weight), continue reaction 2-3 hour, splash into amine and reacted again 2-3 hour in 40-80 ℃ of dropwise addition of acrylic acid or methacrylic acid (stopper that contains its weight 0.05-0.2%), record acid number and be lower than at 10 o'clock, stopped reaction gets required prepolymer, cools off stand-by;
Described Resins, epoxy is the ether of binary or polyphenol or alcohol and the formation of dehydration glycerine, and perhaps the dehydration glyceryl ester of binary or polycarboxylic acid comprises the ether that dihydroxyphenyl propane, bisphenol S, butyleneglycol, TriMethylolPropane(TMP), tetramethylolmethane and two dehydration glycerine form; The ester that phthalic acid, hydrogenation of benzene dioctyl phthalate, kautschin maleic anhydride adduct and two dehydration glycerine form;
Described rosin based: be selected from natural rosin, hydrogenation natural rosin, nilox resin, dimerization, poly rosin or accurately machined above-mentioned rosin, consumption is lower than 40% of epoxy group(ing) mole number;
Described amine: be selected from ammonia, primary amine, can select thanomin, Yi Bingchunan for use, secondary amine: can select diethanolamine, diisopropanolamine (DIPA) for use, consumption is lower than the 5-30% of epoxy group(ing) mole number;
Described catalyzer: can select tertiary amine one thioether system for use, wherein thioether can be selected thio-diethylene glycol or sulfo-di-isopropylene glycol for use, and its consumption is the 0.01-3% of epoxy group(ing) mole number;
Described stopper: can select Resorcinol or dihydroxy-benzene mono-methyl for use, its consumption is the 0.05-0.2% of acrylic acid or the like weight;
(2) alkyd of rosin based modification (methyl) acrylic ester prepolymer;
A. make rosin based and polyvalent alcohol in the presence of acid, alkali or neutral catalyst under nitrogen protection reacting by heating, steam the water of generation simultaneously, treat acid number less than 10, promptly get the polyprotonic acid rosin ester class that average per molecule contains two above hydroxyls;
B. the reacting by heating under nitrogen protection with product among the A and di-carboxylic acid steams the water of generation simultaneously, treats that acid number is lower than 10, promptly generates the polyvalent alcohol di-carboxylic acid rosin ester class of hydroxyl;
C. with the product among A or the B in the presence of magnesium alkoxide, with (methyl) acrylate (Resorcinol that contains the 0.05-0.15% of reaction-ure mixture) heating carrying out transesterify, steam the alcohol of generation simultaneously, form alkyd (methyl) acrylic ester prepolymer of rosin based modification, store stand-by;
D. or A and B two-step reaction are merged into a step react:
Rosin based among the A can be selected from the rosin based described in above-mentioned (1), described polyvalent alcohol, can be selected from tetramethylolmethane, TriMethylolPropane(TMP), dipentaerythritol or trolamine, the mol ratio of reactant is 1: 1, catalyzer can be selected Quilonum Retard or phosphorous acid, its consumption is the 0.1-0.3% of rosin weight, temperature of reaction 200-300 ℃, and reaction times 5-8 hour;
Di-carboxylic acid described in the B select oneself diacid, sebacic acid, kautschin toxilic acid affixture, Tetra hydro Phthalic anhydride or m-phthalic acid, the mol ratio of reactant is 2: 1, temperature of reaction 240-290 ℃, reaction times 2-3 hour;
The product of A or B carries out transesterify with (methyl) acrylate (containing Resorcinol) in 110-130 ℃ among the C in the presence of magnesium methylate, reacted 0.5-2 hour, steam the methyl alcohol of generation simultaneously, the mol ratio 1 of reactant: 6-8, Resorcinol and magnesium methylate consumption respectively are the 0.05-0.1% of reaction-ure mixture.
2) preparation of Photocurable composition:
With (1) or (2) prepared prepolymer, reactive thinner and Photoepolymerizationinitiater initiater in 1 successively by its weight ratio: 1: (1-1.2): (0.001-0.06) mix,
Wherein said reactive thinner can be selected (methyl) acrylic acid or the like for use, comprise: their first, second, fourth, 2-ethyl-hexyl, hydroxyethyl, hydroxypropyl, phenoxy group, phenmethyl, isobornyl, dicyclo amylene oxygen ethyl ester, vinylbenzene or their two kinds or many acrylate, Viscoat 295,1.3-propylene glycol acrylate, butylene glycol diacrylate or Vinylstyrene, consumption is the 0-30% of composition weight; Also can add some non-activated thinners: be selected from ethyl acetate, butylacetate, acetone, methylethylketone, pimelinketone, consumption is the 0-30% of whole solution weight; Wherein said Photoepolymerizationinitiater initiater can be selected for use to comprise benzophenone-trolamine system or alpha-substitution st-yrax ethers, can select the alpha-substitution benzoin ether for use, and the consumption of Photoepolymerizationinitiater initiater is the 0.1-6% of whole polymerization composition.
7, the purposes of Photocurable composition, it is characterized in that, select any Photocurable composition among the claim 1-5 for use, adopt that coating, spray quinoline, dipping and other are any can be attached to composition on true qualities or painted paper, wood, leather, fiber, metal, plastics, pottery, glass, building stones or their product surface, with UV-irradiation 1-60 second, can form film as lacquer, the middle and high pressure mercury lamp of ultraviolet source, every centimetre of radiation flux of fluorescent tube is treated about 10 centimetres of cured article and fluorescent tube distances greater than 80 watts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89100518 CN1028433C (en) | 1989-02-01 | 1989-02-01 | Optical solidification compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89100518 CN1028433C (en) | 1989-02-01 | 1989-02-01 | Optical solidification compound and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044666A CN1044666A (en) | 1990-08-15 |
| CN1028433C true CN1028433C (en) | 1995-05-17 |
Family
ID=4853904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89100518 Expired - Fee Related CN1028433C (en) | 1989-02-01 | 1989-02-01 | Optical solidification compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1028433C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091457C (en) * | 2000-06-07 | 2002-09-25 | 湖南亚大化工建材有限公司 | Ultraviolet cured paint |
| CN1311296C (en) * | 2002-10-23 | 2007-04-18 | 东京应化工业株式会社 | Positive type photo erosion resistant agent composition used for making LCD and forming method of erosion resistant picture |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357366C (en) * | 2003-12-19 | 2007-12-26 | 中国印钞造币总公司 | Surface coating composition |
| WO2005108458A1 (en) * | 2004-05-06 | 2005-11-17 | Jsr Corporation | Curable resin composition, overcoats, and process for formation thereof |
| CN100434892C (en) * | 2005-12-15 | 2008-11-19 | 西安交通大学 | Photo cured resin-metal composite aircraft wind tannel model manufacturing and assembling |
| US20080289750A1 (en) * | 2006-01-13 | 2008-11-27 | Denki Kagaku Kogyo Kabushiki Kaisha | Curable Resin Composition, Surface Protection Method, Temporary Fixation Method, and Separation Method |
| JP5052792B2 (en) * | 2006-01-13 | 2012-10-17 | 電気化学工業株式会社 | Resin composition and method for temporarily fixing and protecting surface of workpiece using the same |
| JP5060474B2 (en) * | 2006-06-02 | 2012-10-31 | 昭和電工株式会社 | Photosensitive resin and photosensitive resin composition |
| CN102746771A (en) * | 2012-05-29 | 2012-10-24 | 兰州理工大学 | Alkyd acrylic graft copolymer paint and preparation method thereof |
| CN103525273A (en) * | 2013-09-30 | 2014-01-22 | 安徽蓝柯复合材料有限公司 | UV (ultraviolet) coating with water drop effect and preparation method thereof |
| CN103555188A (en) * | 2013-10-18 | 2014-02-05 | 安徽蓝柯复合材料有限公司 | UV (ultraviolet) photocuring paint and preparation method thereof |
| CN103540241A (en) * | 2013-10-18 | 2014-01-29 | 安徽蓝柯复合材料有限公司 | Ultraviolet-curing primer wood coating and preparation method thereof |
| CN103952913A (en) * | 2014-05-21 | 2014-07-30 | 张家港市玮美纺织有限公司 | Anti-ultraviolet short fiber yarns |
| CN104164113B (en) * | 2014-09-09 | 2016-06-15 | 苏州圣谱拉新材料科技有限公司 | A kind of pottery unsaturated polyester coating |
| CN104693939A (en) * | 2015-03-12 | 2015-06-10 | 湖州中辰建设有限公司 | Novel radiation-cured acrylic resin powder coating for ceramics |
| CN105255329B (en) * | 2015-11-07 | 2018-04-06 | 浙江华江科技发展有限公司 | A kind of modification bamboo fibre of UV-cured resin cladding and preparation method thereof |
| CN105237689A (en) * | 2015-11-16 | 2016-01-13 | 复旦大学 | Digital light procession photocuring material and preparing method thereof |
| CN108219676B (en) * | 2016-12-22 | 2021-04-27 | 谭海剑 | Special modified rosin resin, preparation method and application thereof |
| CN107090739A (en) * | 2017-04-28 | 2017-08-25 | 常州佳饰家装饰新材料有限公司 | Physics and chemistry film and its preparation method and application its physics and chemistry paper and preparation technology |
| CN108659231B (en) * | 2018-05-03 | 2021-04-27 | 南京工业大学 | Photocuring dendritic rosin alcohol-based resin and preparation method thereof |
-
1989
- 1989-02-01 CN CN 89100518 patent/CN1028433C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091457C (en) * | 2000-06-07 | 2002-09-25 | 湖南亚大化工建材有限公司 | Ultraviolet cured paint |
| CN1311296C (en) * | 2002-10-23 | 2007-04-18 | 东京应化工业株式会社 | Positive type photo erosion resistant agent composition used for making LCD and forming method of erosion resistant picture |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1044666A (en) | 1990-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1028433C (en) | Optical solidification compound and preparation method and application thereof | |
| KR102141769B1 (en) | Hybrid photosensitive resin and its manufacturing method | |
| CN1125456A (en) | Stabilized cationically-curable compositions | |
| CN1177346A (en) | Energy-activatable salt with fluorocarbon anions | |
| CN1708488A (en) | Improvement in the storage stability of photoinitiators | |
| CN101130518A (en) | Ionic liquid photo generated base alkaline agent, preparing method and uses of the same | |
| CN111138290B (en) | Aromatic ring-containing benzophenone derivative and preparation method and application thereof | |
| EP3715381B1 (en) | Dibutylfluorene derivative and application thereof as photoinitiator | |
| CN102436145A (en) | Stereo lithography rapid prototyping photosensitive resin and preparation method thereof | |
| US20150329662A1 (en) | Alkylphenyl derivatives and application thereof as photoinitiator | |
| CN1871200A (en) | White solid photoinitiator in the form of powder and preparation thereof | |
| TW445286B (en) | Radiation-polymerizable composition, film produced thereform and method for forming a coating on a substrate using the composition | |
| JP7245315B2 (en) | EPOXY-MODIFIED ACRYLIC RESIN, PRODUCTION METHOD THEREOF, ENERGY-CURABLE EPOXY-MODIFIED ACRYLIC RESIN-CONTAINING COMPOSITION AND USE | |
| CN115710457B (en) | Ultraviolet light curing composition and preparation method and application thereof | |
| CN114369027B (en) | Itaconic acid diester type photocuring monomer, composition, preparation method and application | |
| SE506958C2 (en) | Photopolymerizable polyester composition and varnish or paint formulation | |
| US20160250136A1 (en) | Uv curable nail coating compositions | |
| CN107075016B (en) | Triacrylate compound and its manufacturing method and composition | |
| CN108794315B (en) | Hybrid photoinitiator and preparation method and application thereof | |
| JPH09235321A (en) | New ester and its use | |
| JPS5930809A (en) | Photo-setting material | |
| JPH01123805A (en) | Photocurable resin composition | |
| CN110713594A (en) | Epoxy modified alkyd resin, preparation method thereof, composition containing epoxy modified alkyd resin and application of composition | |
| CN115417835B (en) | Free radical-cation hybrid monomer derived from oxetane itaconate as well as preparation method and application thereof | |
| CN106588864A (en) | Cyclohexyl dioxolane alcohol methyl methacrylate monomer and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |