CN101440148A - Rosin diacid ester acetal polymer without aryl , process for synthesizing the same and use thereof - Google Patents
Rosin diacid ester acetal polymer without aryl , process for synthesizing the same and use thereof Download PDFInfo
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- CN101440148A CN101440148A CNA200710143982XA CN200710143982A CN101440148A CN 101440148 A CN101440148 A CN 101440148A CN A200710143982X A CNA200710143982X A CN A200710143982XA CN 200710143982 A CN200710143982 A CN 200710143982A CN 101440148 A CN101440148 A CN 101440148A
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- diacid
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Abstract
The invention relates to a rosin diacid ester acetal polymer containing no aryl, and a synthesis method thereof. Rosin diacid comprises propylene pimaric acid and abietic acid dimer, wherein the two acids and various fatty diol divinyl ether compounds are heated and react in the presence of organic solvent so as to obtain a novel ester acetal polymer. As the polymer is easy to undergo acid-caused decomposition reaction, the acetal polymer together with an optical acid production agent can form a novel chemically-amplified positive photoresist material.
Description
Technical field
The technical field of the invention is the macromolecule polymer material field, i.e. novel acetal polymer and the synthetic method thereof of a class.Specifically, colophony diacid and aliphatic dialcohol divinyl ether compound react the formation acetal polymer under certain condition, and this base polymer is easy to take place acid and causes decomposition reaction, but therefore with light acid producing agent constitutional chemistry amplification type photosensitive imaging material.The novel photosensitive imaging material of this class can be used for super large-scale integration with uv positive photoresist (claiming photoresist material again) and printing with Computer To Plate (CTP) sensitization, induced thermal imaging constituent.
Background technology
The image-forming principle of common photo-resist is that alkali-soluble group such as phenolic hydroxyl group and carboxy protective are got up to become acid decomposable from group, as ester group or acetal.These acid decomposable are decomposed under the light acid production from group, and it is solvable to become alkali again, can carry out the dilute alkaline developing imaging.The class New Photoinduced resist system of having reported in recent years is made up of divinyl ether compound and film-forming resin, these divinyl ether compounds comprise aromatic series and aliphatic divinyl ether, and film-forming resin has resol and contains the polymethacrylate derivative of part carboxyl.By the resist rete that these compounds and light acid producing agent are formed, after preliminary drying, phenolic hydroxyl group in the polymkeric substance or carboxyl and divinyl ether compound generation acetalation form crosslinking structure.Dry by the fire through exposure and back again and separate crosslinking reaction, thereby make exposure region have caustic solubility, can obtain positive light anti-etching agent.In order to obtain having the 193nm photo-resist of the fine transparency, can not contain aromatic ring structure, thereby study morely the multipolymer of methacrylic acid system at 193nm.But in order to strengthen the anti-plasma etching ability of photo-resist rete, multipolymer need be introduced a large amount of alicyclic structures, and this has just increased synthetic difficulty.
Inspired by this, we can become the straight chain type acetal polymer by the reaction of diacid and divinyl ether compound at imagination, and this base polymer has sour resolution characteristic, can form positive light anti-etching agent with acidogenic agent etc.Research and selection through to diacid and divinyl ether compound are expected to obtain the novel photic resist of high-performance deep ultraviolet of a class.
Natural rosin mainly is made up of resinous acids such as abietic acids, accounts for 85-90%, is referred to as sylvic acid again.Because it has conjugated double bond, the levopimaric acid in the rosin can generate rosin acrylic acid with vinylformic acid generation diels-alder reaction, and other resinous acid such as abietic acid also isomery turn to levopimaric acid and participate in reaction.Rosin can also obtain polymerized rosin by polymerization reaction take place, mainly is that dimerization reaction generation abietic acid dimer takes place the abietic type acid.More than two kinds of diprotic acid that obtain by rosin reaction, be referred to as colophony diacid.Rosin is small molecules, but has outstanding film-forming properties, and the polynary alicyclic structure of its condensed makes it to be used for photo-resist should have good anti-plasma etching ability.
We can react the generation ester acetal polymer under certain condition by discovering these two kinds of colophony diacids and the various fragrant divinyl ether that is prepared by diphenol, we have proposed patent application (colophony diacid ester aldehyde acetal polyalcohol, its preparation method and use, application number: 200610139248.1) to this class ester acetal compound and preparation method thereof.Further studies show that, colophony diacid also can react the ester acetal polymer that generation does not contain aryl under certain condition with various aliphatic dialcohol divinyl ethers, this class acetal polymer has high acid-decomposed activity, at dark purple outskirt the better transparency is arranged, be suitable for the photic resist of deep ultraviolet and other chemical amplification type photosensitive imaging material.
Therefore, primary study of the present invention the ester acetal polymer that generates of these two kinds of colophony diacids and aliphatic dialcohol divinyl ether compound reaction.
Summary of the invention
On the basis that the reaction of various diacid and divinyl ether compound is studied, we find that colophony diacid and various aliphatic dialcohol divinyl ether compound can react generation straight chain type acetal polymer, this base polymer is soluble in various organic solvents commonly used, has higher softening temperature, Heat stability is good, experiment shows that they easily decompose, discharge carboxyl under acid catalysis under room temperature or heating condition.Base polymer and light acid producing agent etc. can be formed new chemical amplification type positive photoresist together so thus.By selecting the light acid producing agent of different wavelength photoreceptor scopes, can form i line positive photoresist or 248nm (KrF) positive photoresist, also can be used as the image forming material of high sensitivity PS version, CTP plate etc.
Therefore, one aspect of the present invention provides the colophony diacid ester aldehyde acetal polyalcohol shown in a kind of following general formula (I):
R wherein
1Be following various groups, R
1For:
, at this moment, m=1, R
0For-CH
2-or do not have group; R
1For :-CH
2-, at this moment, m≤4, R
0For :-CH
2-; R
1For :-O-, at this moment, m=1, R
0For :-CH
2CH
2-.
R
2Be the rosin acrylic acid that is derived from formula (II) or the dimeric colophony diacid residue of abietic acid of formula (III):
Rosin acrylic acid abietic acid dimer
(II) (III)
The present invention provides the method for colophony diacid ester aldehyde acetal polyalcohol shown in the above-mentioned general formula of a kind of preparation (I) on the other hand, comprises making colophony diacid and aliphatic dialcohol divinyl ether compound reacting by heating and obtain required ester acetal polymer in the presence of organic solvent.
Detailed Description Of The Invention
In the methods of the invention, used colophony diacid comprises the rosin acrylic acid of following formula (II) and the abietic acid dimer of following formula (III):
Rosin acrylic acid abietic acid dimer
(II) (III)
The rosin acrylic acid of formula (II) is made by following reaction by sylvic acid and vinylformic acid:
Levopimaric acid in the sylvic acid can be directly and the vinylformic acid reaction, and other resinous acid elder generation's isomery when reaction is carried out turns to levopimaric acid and reacts with vinylformic acid.
Particularly, the used rosin acrylic acid of the present invention can prepare as follows: commercial superfine or one-level rosin are pressed literature method (Xie Hui, Cheng Zhi, the development of rosin acrylic acid type polyurethane coating, chemistry of forest product and chemical industry, 1998,18 (3), 67-73) with vinylformic acid react rosin acrylic acid.Product can get content at the rosin acrylic acid more than 95% by organic solvent recrystallizations such as benzene.
The abietic acid dimer of formula (III) is obtained by following polymerization by the abietic acid in the rosin:
Polymerized rosin is the important kind of Abietyl modified product, and domestic have numerous manufacturers and a supplier, as the bright prosperous imperial Chemicals company limited of rosin chemical industry company limited, Beijing woods etc. that reaches in Yunan County, Guangdong.Polymerized rosin is based on the abietic acid dimer, and reaction is shown in following formula.The content of dimerization colophonium acid generally is lower than 60% in the polymerized rosin Industrial products, and underpressure distillation is removed unreacted sylvic acid and can be improved its content under high vacuum.Particularly, the used abietic acid dimer of the present invention can prepare as follows: commercial superfine or one-level rosin are pressed literature method (Luo Xinxiang, summer embedding Yin, the preparation of dehydroabietic acid, Yiyang teachers training school journal, 1997,14 (6), 59-60) make abietic acid content and reach sylvic acid about 95%, press literature method (Li Yanlin, Wei rattan children again by isomerization reaction, Liu Xiongmin, the polymerized rosin production technique is improved research, chemical science and technology, 1999,7 (4), 52-55) carry out polyreaction, product boils off unreacted resinous acid under the 1-5mmHg vacuum, can get the abietic acid dimer content at the product more than 90%.Also can adopt the commercially available prod, remove unreacted sylvic acid, obtain the abietic acid dimer and be used for the present invention by methods such as underpressure distillation under the high vacuum.
Yet in the present invention, a small amount of monobasic resinous acid also can be used as reactant and participates in polyreaction, and is little to final polymer property and application influence thereof.The tripolymer that generally also contains minute quantity in the abietic acid dimer, also little to final polymer property and application influence thereof.
In the methods of the invention, the used general available following formula of divinyl ether compound (II) is represented:
R wherein
1, m, R
0Suc as formula defining in (I).
Preferred divinyl ether compound is: 1,4-divinyl oxide ylmethyl hexanaphthene, 1,4-divinyl oxide basic ring hexane, 1,2-divinyl oxide base ethane, 1,3-divinyl oxide base propane, 1,4-divinyl oxide base butane, divinyl oxide benzyl ethyl ethers etc. can be bought the commercially available prod or prepare by literature method.
Colophony diacid and divinyl ether compound reacting by heating in the presence of organic solvent can obtain the colophony diacid ester aldehyde acetal polyalcohol shown in a series of above-mentioned general formulas (I).Reacting used organic solvent is non-polar solvent or weak polar solvents such as pimelinketone, dioxane such as toluene, dimethylbenzene.Solvent load generally can make reactant dissolve fully under reaction conditions and get final product, and solvent is many can be reduced speed of response and cause waste.For example solvent can use with the amount of 25-75 weight % based on the reaction system total amount.Intensive polar solvent such as ethylene glycol ethyl ether, methyl-sulphoxide, N, dinethylformamide etc. cause reacting that difficulty is carried out, extent of polymerization is low even cause side reaction to take place.The reaction Heating temperature is 100-160 ℃, preferred 120-140 ℃.Temperature is low, and then speed of response is slow, and temperature is too high then may to cause side reaction to take place.The reaction mol ratio of raw material colophony diacid and divinyl ether compound is generally 1:1, and perhaps diacid is excessive slightly 10%, and is preferred 5%, if two excessive acids are too many, the alkali-resistivity of resulting polymers is poor, and it is bad to be used for the resist effect.Reaction process can detect with infrared spectra, along with reaction is carried out, and visible 3400cm
-1Near the absorption of carboxylic acid disappears 1690cm substantially
-1Near the carbonyl absorption of carboxylic acid disappears, 1720cm
-1Near the carbonyl absorption of ester group appears.Under preferred reaction conditions, reaction can be finished in 2-8 hour.Obtain ester acetal polymer product solution.This product solution can directly use, and also this product solution can be poured in an amount of sherwood oil or other solvent, separates out the product solid, and drying or vacuum-drying get solid product.
Experiment show ester acetal polymer of the present invention under the strong acid catalysis in room temperature or can decompose rapidly under the heat condition a little, discharge carboxyl, insoluble to become alkali molten by alkali.Therefore, can form new chemical amplification type positive photoresist together by this class ester acetal polymer and light acid producing agent etc.
Embodiment
The present invention is described in detail by the following example, but these embodiment do not limit the scope of the invention.
Reference example 1The preparation of rosin acrylic acid
Getting the commercial superfine rosin of 100g adds in the 500ml four-hole boiling flask of band stirring and condensing works, add the 1g Resorcinol, be heated to 230 ℃, import nitrogen (flow velocity is 60ml/min) simultaneously, dropwise addition of acrylic acid 22g, be incubated 3 hours, cooling is dissolved in 200ml acetone with it, drops in the hot water of 80 ℃ of 600ml, separate out pressed powder, productive rate is 85%, is the dissolving of 4% NaOH solution with pressed powder with the 500ml massfraction, gained solution under agitation Dropwise 5 MHCl solution to pH be 7～8, drip again 1MHCl solution to pH be 6.5, drip again behind the filtering throw out excessive 1MHCl solution to no longer include the precipitation separate out.Throw out is leached again, be neutral with being washed with distilled water to washings behind the 400ml ether dissolution, ether spends the night with anhydrous sodium sulfate drying, gets rosin acrylic acid, productive rate 25% with about 100ml benzene recrystallization.Its outward appearance is a white crystal, and acid number is 300mg KOH/g, and fusing point is 201～203 ℃, and purity is 98%.
Reference example 2The dimeric preparation of abietic acid
Add the commercial superfine rosin of 150g, 250ml 95% ethanol and 10ml concentrated hydrochloric acid in the 500ml single port flask.Reflux 3 hours is cooled to 0 ℃, leaves standstill 4～5 hours, collects the solid of separating out, and is washed till water lotion with distilled water and is neutral, and oven dry gets the 75g sylvic acid, and wherein abietic acid content is near 95%.
In the 500ml there-necked flask, add the sylvic acid that makes more than the 50g, add 60ml toluene, at room temperature stirring and dissolving.Temperature control with 1.5 hours Dropwise 5 ml vitriol oils and 1ml Glacial acetic acid mixture, continues reaction and finished in 2.5 hours about 40 ℃.Add the 200ml dilution with toluene, leave standstill layering in 4 hours.Tell organic phase, with the washing of 0.5% heat (60～80 ℃) salt solution, sulfate radical-free ion in washings (dropping contains barium chloride solution does not on a small quantity have the barium sulfate precipitate generation).Product solution elder generation water circulating vacuum pump pressure reducing and steaming toluene and water boil off unreacted sylvic acid with the oil pump decompression again under the 3-5mmHg vacuum, the remaining product that is, and wherein the dimeric content of abietic acid is 92%.
Embodiment 1Rosin acrylic acid and 1,4-divinyl oxide ylmethyl hexanaphthene (cyclohexyl dimethanol divinyl ether) reaction
In having the 500ml four-hole bottle of mechanical stirring, thermometer, prolong, add rosin acrylic acid and the 19.6g (0.1mol) 1 of 37.4g (0.1mol) from reference example 1,4-divinyl oxide ylmethyl hexanaphthene (cyclohexyl dimethyl divinyl ether), add 60ml dimethylbenzene, heated and stirred makes its dissolving, be warming up to 120-130 ℃, stirring reaction finished in 3 hours.
Product is measured the visible 3400cm of infrared spectra
-1Near the absorption of carboxylic acid disappears 1690cm substantially
-1Near the carbonyl absorption of carboxylic acid disappears, 1720cm
-1Near the carbonyl absorption of ester group appears.Show to react and finish.
Embodiment 2Rosin acrylic acid and divinyl oxide benzyl ethyl ether (glycol ether divinyl ether) reaction
In having the 500ml four-hole bottle of mechanical stirring, thermometer, prolong, add rosin acrylic acid and 15.8g (0.1mol) the divinyl oxide benzyl ethyl ether (glycol ether divinyl ether) of 37.4g (0.1mol) from reference example 1, add 50ml dimethylbenzene, heated and stirred makes its dissolving, be warming up to 120-130 ℃, stirring reaction finished in 3 hours.
Product is measured the visible 3400cm of infrared spectra
-1Near the absorption of carboxylic acid disappears 1690cm substantially
-1Near the carbonyl absorption of carboxylic acid disappears, 1720cm
-1Near the carbonyl absorption of ester group appears.Show to react and finish.
Embodiment 3Dimerization abietic acid and 1,4-divinyl oxide ylmethyl hexanaphthene (cyclohexyl dimethanol divinyl ether) reaction
In having the 500ml four-hole bottle of mechanical stirring, thermometer, prolong, add abietic acid dimer and the 19.6g (0.1mol) 1 of 59.1g (0.1mol) from reference example 2,4-divinyl oxide ylmethyl hexanaphthene (cyclohexyl dimethyl divinyl ether), add 80ml dimethylbenzene, heated and stirred makes its dissolving, be warming up to 120-130 ℃, stirring reaction finished in 3 hours.
Product is measured the visible 3400cm of infrared spectra
-1Near the absorption of carboxylic acid disappears 1690cm substantially
-1Near the carbonyl absorption of carboxylic acid disappears, 1720cm
-1Near the carbonyl absorption of ester group appears.Show to react and finish.
Embodiment 4Dimerization abietic acid and divinyl oxide benzyl ethyl ether (glycol ether divinyl ether) reaction
In having the 500ml four-hole bottle of mechanical stirring, thermometer, prolong, add abietic acid dimer and 15.8g (0.1mol) the divinyl oxide benzyl ethyl ether (glycol ether divinyl ether) of 59.1g (0.1mol) from reference example 2, add the 80ml pimelinketone, heated and stirred makes its dissolving, be warming up to 120-130 ℃, stirring reaction finished in 4 hours.
Product is measured the visible 3400cm of infrared spectra
-1Near the absorption of carboxylic acid disappears 1690cm substantially
-1Near the carbonyl absorption of carboxylic acid disappears, 1720cm
-1Near the carbonyl absorption of ester group appears.Show to react and finish.
Embodiment 5Rosin acrylic acid and 1,2-divinyl oxide base ethane (ethylene glycol bisthioglycolate vinyl ether) reaction
In having the 500ml four-hole bottle of mechanical stirring, thermometer, prolong, add rosin acrylic acid and the 11.4g (0.1mol) 1 of 37.4g (0.1mol) from reference example 1,2-divinyl oxide base ethane (ethylene glycol bisthioglycolate vinyl ether), add the 50ml dioxane, heated and stirred makes its dissolving, be warming up to 120-130 ℃, stirring reaction finished in 4 hours.
Product is measured the visible 3400cm of infrared spectra
-1Near the absorption of carboxylic acid disappears 1690cm substantially
-1Near the carbonyl absorption of carboxylic acid disappears, 1720cm
-1Near the carbonyl absorption of ester group appears.Show to react and finish.
Claims (10)
1. the colophony diacid ester aldehyde acetal polyalcohol shown in the following general formula (I):
R wherein
1Be following various groups, R
1For:
At this moment, m=1, R
0For-CH
2-or do not have group; R
1For :-CH
2-, at this moment, m≤4, R
0For :-CH
2-; R
1For :-O-, at this moment, m=1, R
0For :-CH
2CH
2-.
R wherein
2Be the rosin acrylic acid that is derived from formula (II) or the dimeric colophony diacid residue of abietic acid of formula (III):
Rosin acrylic acid abietic acid dimer
(II) (III)。
2. method for preparing the described polymkeric substance of claim 1 comprises making the reacting by heating and obtaining in the presence of organic solvent of the divinyl ether compound shown in colophony diacid and the following formula (IV):
R wherein
1, m, R
0Suc as formula defining in (I).
3. method as claimed in claim 2, wherein said colophony diacid are the rosin acrylic acid of following formula (II) or the abietic acid dimer of following formula (III):
Rosin acrylic acid abietic acid dimer
(II) (III)。
4. method as claimed in claim 2, wherein used divinyl ether compound comprises: 1,4-divinyl oxide ylmethyl hexanaphthene, 1,4-divinyl oxide basic ring hexane, 1,2-divinyl oxide base ethane, 1,3-divinyl oxide base propane, 1,4-divinyl oxide base butane, divinyl oxide benzyl ethyl ether.
5. method as claimed in claim 2, wherein said solvent are non-polar solvent or weak polar solvents such as pimelinketone, dioxane such as toluene, dimethylbenzene.
6. method as claimed in claim 5, the consumption of solvent is 25-75 weight % based on the reaction system total amount.
7. method as claimed in claim 2, wherein said Heating temperature are 100-160 ℃.
8. method as claimed in claim 6, wherein said Heating temperature are that 120-140 ℃ and reaction times are 2-6 hour.
9. method as claimed in claim 2, wherein the mol ratio of diacid and divinyl ether compound is 1-1.1:1.
10. method as claimed in claim 8, wherein the mol ratio of diacid and divinyl ether compound is 1-1.05:1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710143982XA CN101440148A (en) | 2007-08-17 | 2007-08-17 | Rosin diacid ester acetal polymer without aryl , process for synthesizing the same and use thereof |
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|---|---|---|---|
| CNA200710143982XA CN101440148A (en) | 2007-08-17 | 2007-08-17 | Rosin diacid ester acetal polymer without aryl , process for synthesizing the same and use thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812173A (en) * | 2009-11-05 | 2010-08-25 | 北京师范大学 | N-hydroxy maleopimaric acid imide ester acetal polymer and preparation method thereof |
| CN104181775A (en) * | 2014-08-18 | 2014-12-03 | 邯郸开发区立业化工有限公司 | Chemically amplified i-line positive photoresist composition containing diphenol acetal polymer |
-
2007
- 2007-08-17 CN CNA200710143982XA patent/CN101440148A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812173A (en) * | 2009-11-05 | 2010-08-25 | 北京师范大学 | N-hydroxy maleopimaric acid imide ester acetal polymer and preparation method thereof |
| CN101812173B (en) * | 2009-11-05 | 2014-01-29 | 北京师范大学 | N-hydroxy maleopimaric acid imide ester acetal polymer and preparation method thereof |
| CN104181775A (en) * | 2014-08-18 | 2014-12-03 | 邯郸开发区立业化工有限公司 | Chemically amplified i-line positive photoresist composition containing diphenol acetal polymer |
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Open date: 20090527 |