CN101172951B - Hydroxyl-oxethyl-diphenyl-ketone carboxylic acid ester and use as photo-initiation agent thereof - Google Patents
Hydroxyl-oxethyl-diphenyl-ketone carboxylic acid ester and use as photo-initiation agent thereof Download PDFInfo
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Abstract
The invention provides compounds illustrated in the formulation (1), wherein, n is equal to or larger than 6 and is equal to or less than 10. The invention also provides the uses that the compound can be used as photo initiator.
Description
Technical field
The present invention relates to a class hydroxyl-oxethyl-diphenyl-ketone carboxylic acid ester compound.This compound can be used as light trigger, especially for the varnish of UV photocuring, printing-ink etc.The present invention also provides and comprises the radiation-curable composition of at least a compound of the present invention as light trigger.
Background technology
The light trigger that is used for lacquer formulation need possess good curing speed, particularly surface of good curing activity, low smell, low yellowness factor and good solubleness.In addition, along with the human consumer to external compound polluted responsive day by day in the food, be to observe the following legislation requirement that may formulate, the migration of compound with also should be as far as possible little by external agency dissolved tendency.The commercial goods light trigger more and more is difficult to satisfy above every requirement at present.
At present, benzophenone remains ultraviolet ray (UV) and solidifies the most widely used light trigger of overprint varnish zhe, and is simultaneously cheap again because its surface cure is good, solubleness is big, obtains easily.But the benzophenone smell is strong, and as easy as rolling off a log from printed matter the migration and dissolved separating out.
As everyone knows, polyfunctional benzophenone derivates can produce some low smells, be not easy to occur to move and the product of dissolved phenomenon, but these products have the low shortcoming of effective component content, and and then cause curing speed lower, simultaneously because the synthetic difficulty causes price higher.
This shows that solidified coating, migration and the dissolved tendency that good solubility, height reactive behavior can be arranged, can produce extremely low smell in formulation for coating material are significantly less than most of light triggers that have benzophenone compounds now and exist current demand.
We find that now a class meets the The compounds of this invention of above-mentioned requirements.The connection chain group of this compounds makes it have good solubleness in the ultraviolet curing prescription.The unit weight reactive behavior of light trigger is of crucial importance in ultra-violet curing.If a kind of reactive behavior of light trigger is lower than benzophenone, can strengthen the curing speed of consumption, but effect is limited to keep filling a prescription.In addition, after concentration surpassed 10～12%, the non-acrylate official can material or is demonstrated the character of softening agent, perhaps reduces the cross-linking density of cured film, so that influences its mechanical property.The compounds of this invention has not only overcome the above-mentioned defective of benzophenone and other existing light trigger, have smell extremely low, in ultraviolet curing prescription solubleness height, migration and by the little advantage of external agency tendency, in most of the cases, its reactive behavior is higher than normally used benzophenone surrogate.
Summary of the invention
The invention provides the compound shown in the formula (I),
Wherein,
6≤n≤16, n is an integer;
Consider accessibility and economy, often also use the multiple mixture that meets the compound of formula (I) definition in the practice.Therefore, the present invention also provides a kind of photoinitiator composite, it is characterized in that said composition is made up of with arbitrary proportion two or more compound of formula (I).
In addition, the present invention also provides the purposes of the compound of formula (I) as light trigger.
In addition, the present invention also provides a kind of energy-curable liquid composition, and said composition contains following compositions:
Polymerisable composition wherein comprises a kind of ethylenically unsaturated monomer or oligomer at least;
Formula of the present invention (I) light trigger.
The present invention also provides energy-curable liquid composition of the present invention is placed under the radiation, especially under the ultraviolet radiation, prepares the method for cured polymer.
In formula of the present invention (I), the Sauerstoffatom that is connected on the phenyl of benzophenone can be connected on the optional position of phenyl.Consider that the being easy to get property of raw material and synthetic are convenient, preferred described Sauerstoffatom is connected on the ortho position or contraposition for benzophenone.The difference of link position is to the character of compound, and especially the character as light trigger does not have materially affect.
In formula of the present invention (I) compound, (CH
2)
nBe linear chain structure.
N is preferably 6,7 or 8; Most preferably be 8.
Compound of the present invention can adopt the well-known method of preparation ester compound to be prepared, and selected definite synthetic route and reaction conditions depend on the compound that will prepare.
For example, The compounds of this invention can pass through formula (II) and CH
3(CH
2)
nThe COOH esterification is prepared.
Reaction is preferably carried out under the condition that solvent exists, and the character of solvent place not essential to the present invention is as long as it has no adverse effects to reagent or reaction.The solvent that is fit to comprises: alkane, for example hexanaphthene etc.; Aromatic hydrocarbons, for example benzene, toluene or dimethylbenzene etc.
Reaction is for example carried out under the existence of sulfonic acid (for example tosic acid or methylsulfonic acid), mineral acid (for example sulfuric acid, hydrochloric acid or polyphosphoric acid) or Lewis acid (for example boron trifluoride or organic titanate) preferably at an acidic catalyst.
Temperature of reaction can change in quite on a large scale, and this depends on the condition of reaction and the character of reagent and solvent, as long as the water that temperature is high enough to remove in the reaction process to be produced gets final product to guarantee that reaction is finished.We find to react the most convenient usually under near the reaction mixture refluxed temperature.The reaction required time has very big difference, and this depends primarily on temperature of reaction.Under above-mentioned optimal conditions, only need reaction 2～20 hours usually.
After reaction was finished, available ordinary method was carried out aftertreatment, and for example water and/or soda lye wash mixture are dried, and solvent evaporated under reduced pressure obtains product then, and solid product can be used the appropriate solvent crystallization.
The compounds of this invention is especially suitable for use as light trigger, and one or more mixtures are used for the varnish or the printing ink of photocuring separately.But they also can be used among many other energy-curable liquid compositions.
Adopt the energy-curable composition of The compounds of this invention to generally include at least a radiation curable monomer and/or oligomer, The compounds of this invention, and can choose wantonly and also comprise a kind of reactive thinner.With regard to printing-ink, described composition also comprises colorant, i.e. pigment.Radiation curable monomer or oligomer be alefinically unsaturated compounds preferably, is generally acrylate oligomer or acrylate monomer.The acrylate oligomer that is fit to comprises: aliphatics or aromatics propenoic methyl carbamate, polyether acrylate, polyester acrylate and epoxy acrylate (for example outer bisphenol A epoxy acrylate).The acrylate monomer that is fit to comprises: hexylene glycol double methacrylate, Viscoat 295, ditrimethylolpropane tetraacrylate, double pentaerythritol C5 methacrylate, polyether acrylate (for example ethoxylated trimethylolpropane triacrylate, the glycerol base third oxidation triacrylate, ethoxylation tetramethylol methane tetraacrylate), and epoxy acrylate (as the Ebcryl 150 of USB company), and diol acrylate (for example tri-propanediol diacrylate).
Simultaneously, energy-curable composition of the present invention preferably comprises a kind of synergistic agent at least, for example a kind of amino acrylates or a kind of dimethylaminobenzoic acid ester.With regard to printing-ink, synergistic agent is the dimethylaminobenzoic acid ester preferably, and with regard to varnish, synergistic agent is amino acrylates preferably.Some printing ink for example is used for the printing ink of flexographic printing purposes, can contain above-mentioned two kinds of dissimilar synergistic agent.
What of radiation curable monomer or oligomer, light trigger, synergistic agent and optional colorant consumption are different because of the type of varnish or printing ink, the concrete equipment and the purposes that are used to apply.But under typical situation, the light trigger consumption is 2～20% of a composition total weight.
Formula (I) compound except the above composition, also comprises pigment, wax, stablizer and auxiliary rheological agents usually when being used for varnish or printing ink as light trigger.
Embodiment
The present invention can be further described with following indefiniteness embodiment.
Comparative examples
In the 250ml four-hole boiling flask, add the 100g lauric acid, be warming up to 50 ℃, treat to open stirring after the lauric acid dissolving, keep temperature of reaction below 75 ℃, beginning slowly splashes into thionyl chloride 45ml.Back flow reaction is 2 hours then.Stopped reaction keeps the liquid temperature between 90～100 ℃, and unreacted thionyl chloride is sloughed in the water pump decompression.Decompression is collected temperature and is the lauric acid acyl chlorides at the cut of 146～150 ℃/16～17mmHg, and outward appearance is a colourless transparent liquid, is total to 84.5g, productive rate 77.3%.
(connect one CaCl is housed at the 100ml reaction flask
2Drying tube) in, add 4-hydroxyl-benzophenone and 20ml anhydrous pyridine and the mixing of 20.0g (0.099mol).The lauric acid acyl chlorides 24ml that in 10 minutes, dropwise adds (0.101mol) then.The temperature of this reaction can rise by nature, and has yellow mercury oxide to generate.When temperature of reaction no longer rises, reaction mixture is poured under stirring fast in 3% the hydrochloric acid that 600ml contains trash ice.Product with the 20ml washing, is washed with 20ml methyl alcohol earlier after B filters again.At room temperature collect and drying products.With obtaining the 32.2g white powder after the recrystallizing methanol of 180ml, productive rate is 85.3% again.Fusing point is: 47.5～49.5 ℃.
Embodiment 1
The four-hole bottle of 1000ml adds aluminum chloride 112g (0.84mol), and 1,2 ethylene dichloride 300ml stirs when being cooled to 0～-5 ℃, adds ethylene glycol phenyl ether acetate 72.1g (0.4mol) on a small quantity repeatedly, and temperature slightly raises; When temperature is reduced to 0～-5 ℃, begin to drip Benzoyl chloride 67.5g (0.48mol), drip after the back continues reaction 1h, feed liquid is poured in 200ml concentrated hydrochloric acid and the 500ml frozen water stir hydrolysis, the solution left standstill layering; Oil phase adds the 200ml water washing again, when oil phase decompression precipitation is done soon to solvent, dropping 100ml concentration is 15% liquid caustic soda in reaction flask, and control liquid temperature is slowly lowered the temperature after dripping off at 75～80 ℃, the liquid temperature drop is to about 30 ℃, add the extraction of 200ml ethylene dichloride to system, standing demix is told oil phase and is added the 200ml water washing, get oil phase and carry out reflux dewatering, decrease temperature crystalline; Suction filtration gets white solid, dries heavy 81.8g, and purity is greater than 99%, productive rate 84.42%; Fusing point: 80.9～81.9 ℃.
1HNMR(δ，ppm)：4.01(t，CH
2)，4.18(t，CH
2)，7.00(d，Ar-)，7.47(t，Ar-)，7.57(t，Ar-)，7.74(d，Ar-)，7.82(d，Ar-).
Embodiment 2
Get a 250ml four-hole bottle, place 100 milliliters of toluene to carry out the azeotropic back flow reaction 10 hours 10.0 gram (0.041mol) Compound I I, 8.52 gram (0.043mol) laurostearic acids and 0.4 gram tosic acid.Reaction solution adds the aqueous solution that 100 ml contain 1.0 gram sodium bicarbonates, and stirring at room 0.5 hour is told water, upper toluene solution deionized water 100ml washed twice.Reflux dewatering then, heat filter decrease temperature crystalline ,-5 ℃ of suction filtrations obtain white solid, dry the 14.3g that weighs, yield 82.1%, purity 99.12%, fusing point is: 59.1～60.8 ℃.
1HNMR(δ，ppm)：0.87(t，CH
3)，1.25(s，CH
2)，1.64(m，CH
2)，2.36(t，CH
2)，4.26(t，CH
2)，4.47(t，CH
2)，6.96(d，Ar-)，7.47(t，Ar-)，7.55(t，Ar-)，7.75(d，Ar-).7.82(d，Ar-).
Embodiment 3
The four-hole bottle of 250mL adds 10.5g (0.043mol) Compound I I, capric acid 7.7g (0.045mol), and tosic acid 0.5g, toluene 100ml stirs, and carries out azeotropic back flow reaction 8h, stirs to be cooled to room temperature, adds 1%NaHCO
3Aqueous solution 100ml keeps stirring at room 0.5h; Layering, 100ml * 2 water washings of upper toluene solution, standing demix; Gained upper strata light yellow oil subtracts each other pressure-off and falls partial solvent, and the about 60ml of surplus solution pours in the triangular flask, puts into refrigerator and cooled and freezes and spend the night, and the adularescent solid is separated out; Suction filtration gets white solid 12.7g, yield 74.5%, and purity 99.25%, fusing point is: 50.3～50.9 ℃.
1HNMR(δ，ppm)：0.87(t，CH
3)，1.25(d，CH
2)，1.64(m，CH
2)，2.36(t，CH
2)，4.26(t，CH
2)，4.47(t，CH
2)，6.96(d，Ar-)，7.47(t，Ar-)，7.57(tAr-)，7.74(d，Ar-).7.81(d，Ar-)。
The compound source is summarized in table one
Table one
| Material name | Supplier |
| 4-hydroxyl-benzophenone | The emerging medication chemistry of Hubei section |
| The ethylene glycol phenyl ether acetate | Shanghai Jin Shan chemical industry |
| Laurostearic acid (month capric acid) | Xu Dong chemical plant, Beijing |
| Capric acid | Xing Jin chemical plant, Beijing |
| Ethylene dichloride | Modern east, Beijing fine chemicals company limited |
| Thionyl chloride | Beijing chemical reagents corporation |
| Anhydrous pyridine | Tianjin chemical reagent three factories |
| Hydrochloric acid | Beijing northization is meticulous |
| Tosic acid | Beijing chemical reagents corporation |
| Toluene | Jin Yuan chemical plant, Zhou village, Zibo City |
| Methyl alcohol | Beijing chemical reagents corporation |
| Sodium bicarbonate | Beijing chemical reagents corporation |
| Benzophenone | Beijing chemical reagents corporation |
Embodiment 4
Curing performance relatively
Will by the foregoing description two and three and the light trigger of comparing embodiment institute described method preparation respectively make a ultraviolet curing varnish preparation, the prescription of described preparation sees Table two
Table two
| System component | Per-cent (%) |
| Light trigger | 7 |
| 6145-100 (Changxing, Taiwan company) | 32 |
| EO3-TMPTA (Tianjin proud son of heaven chemical industry) | 28 |
| HDDA (Tianjin proud son of heaven chemical industry) | 28 |
| 4-dimethyl ethyl aminobenzoate (Beijing English power is refined) | 5 |
The varnish of preparation being executed printing on the tinplate with the excellent spreader of 10 micro wires, is that the medium pressure mercury Jupiter is cured with 100 meters/component velocity in 60 watts/centimetre with a power.Record obtains surface of good and thoroughly solidifies number of pass times under the needed lamp.Smell is 5 grades to the maximum, and minimum is 1 grade.Huang Du is measured by the full-automatic color difference meter of SC-80C.The result as shown in Table 3.
Table three
| Light trigger | The required number of pass times of completely solidified | The smell grading | Huang Du |
| Benzophenone | 4 | 5 | 0.55 |
| Comparative examples | 6 | 2 | 0.56 |
| Embodiment 2 | 5 | 2 | 0.55 |
| Embodiment 3 | 5 | 2 | 0.55 |
The result shows the curing speed fast 20% of compound of the present invention compare embodiment with regard to curing speed.Stink after The compounds of this invention solidifies significantly is lower than benzophenone.Yellowness factor after all examples solidify is all close.
Claims (7)
1. the compound shown in the formula (I):
Wherein,
6≤n≤16, n is an integer.
2. according to the compound of claim 1, wherein n is 8.
3. claim 1 or 2 compound are as the purposes of light trigger.
4. photoinitiator composite is characterized in that it contains formula described at least two kinds of claims 1 (I) combination of compounds.
5. energy-curable liquid composition is characterized in that it contains following compositions:
Polymerisable composition wherein comprises a kind of ethylenically unsaturated monomers or oligomer at least;
Claim 1 or 2 described compounds.
6. the described energy-curable liquid composition of claim 5, described composition is varnish or printing-ink.
7. a method for preparing the solidified polymeric composition comprises claim 5 or 6 described energy-curable liquid compositions are exposed under the ultraviolet radiation.
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| CN2006101142240A CN101172951B (en) | 2006-11-02 | 2006-11-02 | Hydroxyl-oxethyl-diphenyl-ketone carboxylic acid ester and use as photo-initiation agent thereof |
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| CN101172951B true CN101172951B (en) | 2011-08-10 |
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| CN102260358B (en) * | 2010-05-31 | 2012-10-03 | 江苏英力科技发展有限公司 | Use of 2-methoxy-4'-benzoylbiphenyl as photoinitiator |
| CN102958946B (en) | 2011-07-29 | 2014-03-26 | 北京英力科技发展有限公司 | Mercapto-benzophenone compounds, compositions and preparation methods thereof |
| CN103664590A (en) * | 2013-12-20 | 2014-03-26 | 广东鑫钰新材料股份有限公司 | Method for synthesizing compound containing 4-(2-hydroxy ethoxy) diphenylketone structure or acetate thereof |
| CN106478420B (en) * | 2016-09-27 | 2019-02-01 | 四川泸天化股份有限公司 | A method of recycling 4- dihydroxy benaophenonel laurate |
| WO2018090354A1 (en) * | 2016-11-21 | 2018-05-24 | 北京英力科技发展有限公司 | Photocurable composition without benzene release |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4861916A (en) * | 1985-04-03 | 1989-08-29 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Photoinitiators for photopolymerization of unsaturated systems |
| CN1727321A (en) * | 2005-01-04 | 2006-02-01 | 常州华钛化学有限公司 | Multi functional radicles ketonic compound served as photoinitiator, and preparation method |
| CN1796421A (en) * | 2004-12-29 | 2006-07-05 | 国家淀粉及化学投资控股公司 | Photoinitiators and UV-crosslinkable acrylic polymers for pressure sensitive adhesives |
-
2006
- 2006-11-02 CN CN2006101142240A patent/CN101172951B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4861916A (en) * | 1985-04-03 | 1989-08-29 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Photoinitiators for photopolymerization of unsaturated systems |
| CN1796421A (en) * | 2004-12-29 | 2006-07-05 | 国家淀粉及化学投资控股公司 | Photoinitiators and UV-crosslinkable acrylic polymers for pressure sensitive adhesives |
| CN1727321A (en) * | 2005-01-04 | 2006-02-01 | 常州华钛化学有限公司 | Multi functional radicles ketonic compound served as photoinitiator, and preparation method |
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