CN86108059A - Polyhutadiene is eurymeric resist and synthetic method - Google Patents

Abstract

The invention belongs to polyhutadiene and be the photosensitive polymer synthesis method and thus product prepare the eurymeric resist.Because the structure of this product had not only had rubber to be high polymer main chain but also to make its phenolic hydroxyl group with q.s or carboxyl when side chain imports a plurality of diazo naphthoquinone alkylsulfonyls; mix with resol etc. do to have overcome when resist uses that the eurymeric resist film forming properties of being made up of low molecule phenolic ester compound or general photosensitive polymer is poor, shortcoming that low-temperature performance and anti acid alkali performance can differ from, keep the advantage of eurymeric resist resolving power height, water system development and anti-plasma etching simultaneously.Can be widely used in unicircuit resist and PS version sensitizer.

Description

The invention belongs to polyhutadiene and be the synthetic method of photosensitive polymer and thus photosensitive polymer prepare eurymeric resist constituent.

Obtain photosensitive sulphonate and sulphonamide with diazo naphthoquinone SULPHURYL CHLORIDE and alcohols, phenols and amine organic compound reaction and be widely used in electronic industry and Printing industry with resist and printing lithographic plate PS version with the main component of sensitizer as large-scale integrated circuit, and in constantly researching and developing.The resist product overwhelming majority who forms with this class photosensitivity material is made of low molecule polyatomic phenol synthetic phenolic ester compound, for example gallic acid monoesters (JP51-139402A) etc.The resol of phenols such as gained diazonium naphthoquinone sulphonate and meta-cresol mixes does to also have following shortcoming when resist uses:

1. film forming properties is poor, and is crisp, and poor toughness particularly is unsuitable for precoating on soft flexibility sheet base.

2. low-temperature performance is bad, remains to be improved with the adhesiveproperties of some base materials.

3. resistance to acid deficiency, alkali-resistivity is poorer, does not particularly almost have use value as alkaline resist.

Someone imports the diazo naphthoquinone sulfonic group in meta-cresol resol (US 3046120) and the poly(4-hydroxystyrene) polymers such as (JP50-113305A) and has obtained polymer eurymeric resist, but above-mentioned shortcoming does not mostly overcome.

It is polymer that the present invention develops into rubber from general photosensitive polymer, and the gallic acid monoesters is developed into polyester.Purpose is synthetic a kind of like this photosensitive polymer, and on structure, it had both had rubber is high molecular main chain, makes its phenolic hydroxyl group with q.s or carboxyl again when side chain imports a plurality of diazo naphthoquinone alkylsulfonyls.And to utilize this photosensitive polymer to make a kind of rubber be eurymeric resist constituent.This resist have rubber be the negative resist characteristics to overcome the shortcoming of above-mentioned eurymeric resist, keep the advantage of eurymeric resist simultaneously.

The invention is characterized in 1 of weight-average molecular weight 1000～3000, oxirane value 0.3-0.6,2-polyhutadiene epoxy compounds and roll into a ball equimolar gallic acid at carboxylic acid-epoxies catalyzer such as N with epoxy, under the effect of N-dimethyl benzylamine, with appropriate solvent as 1,4-dioxane etc. obtain the polyhutadiene gallic acid ester of following structural formula (I) under 100～130 ℃ temperature of reaction:

〔Ⅰ〕

In the formula, n+m=15-45

n/m＝2-4

Obtain the compound carboxylate of following structural formula (II) again with anhydrides compound such as acetic anhydride esterification:

In the formula, n+m=15-45

n/m＝2-4

And then under the effect of alkaline dehydrohalogenating agent, obtain the high molecular synthetic method of positive light sensitivity of following structural formula (III) more respectively with the diazo naphthoquinone SULPHURYL CHLORIDE of different ratios by (I) (II):

n+m＝15-45

n/m＝2-4。

And to utilize this positive light sensitivity polymer and bonding polymer such as meta-cresol resol and organic solvent such as ethylene glycol monoemethyl ether to mix the composition polyhutadiene be the eurymeric resist.

Used epoxidation 1, the general weight-average molecular weight of 2-polyhutadiene is 1000～3000.Reaction difficulty when molecular weight is too big, the developing performance of product is bad: molecular weight too hour product lacks necessary toughness, and softening temperature is too low, influences the coating film forming operation.Test shows, preferably select for use weight-average molecular weight be 1000～1500 1,2-epoxy polyhutadiene.Its oxirane value is between 0.3～0.6.Oxirane value is too low, and the ratio that then imports gallic acid is also low, causes that sensitization base and phenolic hydroxyl group ratio all descend in the end product, has both influenced photosensitive property, is difficult to again develop with diluted alkaline; Be easy to crosslinking curing in the building-up reactions when oxirane value is too high, so the actual oxirane value of selecting for use is between 0.4～0.5.

Used gallic acid does not preferably have crystal water, and purity is at the product more than 98%.There is the higher product of purity of crystal water also can use.Consumption should be identical or close with the mole number of epoxy group.Consumption can be residual very little the time epoxy group, the reaction later stage is easy to gelling, the liquid alkali developing performance of end product is bad: the residual gallic acid of meeting was in reaction product when consumption was too much, do not go down then to generate the diazonium naphthoquinone sulphonate of a part of gallic acid if do not separate the purifying successive reaction, the product alkali resistance is descended significantly, grievous injury corrosion stability and resolving power.When making the PS version, the oleophylic China ink is exhausted.

Used carboxylic acid-epoxy reaction catalyzer can be used habitual various catalyzer such as N, tertiary amine class materials such as N-dimethyl benzylamine, quaternary ammonium salts such as tetramethyl ammonium chloride, trimethyldodecane ammonium chloride, organometallic compound such as dibutyl tin laurate and some inorganic salt, mineral acid etc.The present invention has selected N for use, the N-dimethyl benzylamine.Consumption is 0.1～5% of an epoxy compounds weight.

Solvent for use has 1,4-dioxane, tetrahydrofuran (THF), methyl-sulphoxide, dimethyl formamide, butanone etc., but from carrying out polystep reaction continuously, wash separated product at last and consider that select 1 for use, the 4-dioxane is better.

For resistance to acid and the oleophylic China ink that improves resist, wish the alcoholic extract hydroxyl group esterification is fallen.Can select for use acetic anhydride, Benzoyl chloride, Acetyl Chloride 98Min., Tetra hydro Phthalic anhydride, maleated rosin, Tetra Hydro Phthalic Anhydride etc. as esterifying agent.Test shows, selects that to roll into a ball equimolar acetic anhydride effect best with epoxy for use.Cost is low, and speed of response is fast, importing rate height.With anhydride esterifying temperature such as acetic anhydride generally at 40～80 ℃.Import anhydride phthalic acid or Tetra Hydro Phthalic Anhydride and can prevent dirty and raising sensitivity on the bottom effectively; But because the steric restriction effect, the importing rate is lower, and relatively poor as PS version sensitizer oleophylic China ink (sense fat).

When importing the diazo naphthoquinone sulfonic group, 1,2,4 bodies of diazo naphthoquinone SULPHURYL CHLORIDE, 2,1,4 bodies and 2,1,5 body all can use, but is easy to get from raw material, and is with low cost, the purity height, good stability, overall targets such as sensitivity and resolving power are considered, have preferentially been selected 2,1 for use, 5-diazo naphthoquinone SULPHURYL CHLORIDE.Test shows that its purity is very big to the performance impact of reacting final product, must select for use fusing point person more than 125 ℃, preferably selects purity＞98% for use, and fusing point is at 130～132 ℃ pure product.Its importing rate is also very big to the property effect of end product, when the hydroxyl in intermediate (I), (II) have more than 2/3 with the reaction of diazo naphthoquinone SULPHURYL CHLORIDE after, even fully exposure of product also is difficult to develop with diluted alkaline, resolving power descends significantly, the corresponding reduction of sensitivity.When the importing rate less than 1/4 the time, alkali-resistivity too a little less than, rete attenuate during development, corrosion stability and resolving power descend.So the importing rate preferably is controlled between 1/3～1/2.

Alkalescence is taken off the HCl material three major types.One class is an inorganic base, as sodium bicarbonate, yellow soda ash, tertiary sodium phosphate, water glass; Another kind of is organic acid alkali metal salt, as sodium-acetate, Sodium propanecarboxylate, sodium ethylene diamine tetracetate, sodium tartrate etc.; The 3rd class is organic bases, as triethylamine, triethylenediamine, hexamethylenetetramine, Tetramethylammonium hydroxide, carbon water ammonium, ammoniacal liquor etc.When synthesizing as PS version sensitizer, yellow soda ash with about 10% or saturated aqueous solution of sodium bicarbonate; When synthesizing, use organic bases, stay in the resist to avoid mineral ion impurity as resist.Add alkali and take dripping method gradually, control rate of addition reaction system PH is remained on below 7, alkali consumption and diazo naphthoquinone SULPHURYL CHLORIDE equivalent.(under situation, should consider the acetous alkali number of neutralization) with the acetic anhydride esterification.

The resist constituent is that positive light sensitivity polymer (III) and bonding polymer (blending polymer) and organic solvent are formed by above-mentioned polyhutadiene.Add a small amount of dyestuff and tensio-active agent etc. in case of necessity.

The bonding polymer can select for use resol class, poly(4-hydroxystyrene) class, PVA to encircle the polymers such as affixture of contract hydroxy benzaldehyde class, epoxy polyhutadiene and hydroxy-benzoic acid.Wherein meta-cresol resol abundant raw material is cheap, and compatibility is good: gained constituent sensitivity, and resolving power, over-all propertieies such as corrosion stability are good.Consumption is 1～3 times of photosensitive polymer.

Solvent can be used ethylene glycol monoemethyl ether, ethylene glycol monomethyl ether, dioxane, N-BUTYL ACETATE etc.Use separately or mix to use and all can.Consumption is different because of the operation of filming.Generally be to be modulated into 5%～10% of solids constituent.

When adopting meta-cresol resol to be the bonding molecule, when ethylene glycol monoemethyl ether was solvent, its composition weight ratio was:

1 polyhutadiene is positive light sensitivity polymer (III)

1-3 meta-cresol resol

The 18-36 ethylene glycol monoemethyl ether.

Its best weight ratio of forming is:

1 polyhutadiene is positive light sensitivity polymer (III)

1.5～2.5 meta-cresol resol

22.5～31.5 ethylene glycol monoemethyl ethers.

Polyhutadiene of the present invention is that the eurymeric resist is that photosensitive polymer possesses the constitutional features that rubber is minus and eurymeric resist simultaneously because of its main ingredient polyhutadiene, thereby making it both have ordinary rubber is that the negative resist solvent nature is good, film forming is easy, strong adhesion, tenacity is good, advantages such as advantages such as anti acid alkali performance is strong have eurymeric resist resolving power height again, and water system development and anti-plasma etching performance are strong.Overcome the existing shortcoming of present photosensitivity eurymeric resist.

Synthesis example 1

Having agitator, the reflux water-dividing device, add oxirane value 0.4 in the there-necked flask of thermometer, weight-average molecular weight be 1000 1,1 mole of the suitable epoxy of 2-polyhutadiene epoxy 250g(group), gallic acid 190g(1 molar hydrate), 1,4-dioxane 500ml, N, N-dimethyl benzylamine 2.5-3g stirs and is warming up to reflux temperature, by emitting from the reflux water-dividing mouth or adding 1, the method of 4-dioxane, 105～110 ℃ of reactions of control reaction temperature 3 hours improve temperature of reaction to 120 ℃ reaction 1 hour then, make reactant become yellow transparent mucus, sampling is applied to skim on the sheet glass, hot blast drying remains transparent solid cladding fully, and is fully solvable and transparent with the 1%NaOH dissolving, can be cooled to 50 ℃ of dischargings and obtain intermediate (I-1).

Synthesis example 2

The method of use-case 1, using the 250g weight-average molecular weight instead is 2000, oxirane value be 0.4 1,2-polyhutadiene epoxy obtains product (I-2), it is still solvable in buck, dissolution rate (I-1) is slow.

Synthesis example 3

The method of use-case 1, using the 250g weight-average molecular weight instead is 2600, oxirane value be 0.4 1,2-polyhutadiene epoxy obtains product (I-3), product self is not too transparent, can not thoroughly dissolve in buck.

Synthesis example 4

The method of use-case 1, use oxirane value instead and be 0.5 1,2-polyhutadiene epoxy 200g(weight-average molecular weight is 1000), other feed intake and reaction conditions constant, obtain product (I-4), it is easily molten and transparent in diluted alkaline water.

Synthesis example 5

The method of use-case 1, use oxirane value instead and be 0.33 1,2-polyhutadiene epoxy 300g(weight-average molecular weight 1000), other feed intake and reaction conditions constant, obtain translucent product (I-5), it is indissoluble in buck, and is solvable in ethanol-dioxane-buck.

Synthesis example 6

Above-mentioned intermediate (I-1) is cooled to 50 ℃ of not dischargings, adds 112g acetic anhydride (1.1mol), and then promptly obtained intermediate (II-1) in 1 hour 60～80 ℃ of reactions 50～60 ℃ of reactions about 2～4 hours.Intermediate (II-1) can inject 20 times of deionized waters or distilled water, stirs, and precipitation is filtered and washed kept dry then; Also can not add separation, directly carry out next step building-up reactions.

Synthesis example 7-10

With the same method of synthesis example 6, can be by synthetic respectively intermediate (II-2)-(II-5) that obtain of intermediate product (I-2)-(I-5) of synthesis example 2-example 5.The wherein available diluted alkaline dissolving of (II-1), (II-4), (II-2) can be in buck dispersion and emulsion, (II-3), (II-5) are insoluble in buck, dissolve in organic solvents such as dioxane.

Synthesis example 11

With synthesis example 1 gained intermediate (I-1) 0.1mol(solid meter 44g), add acetone 350g, 2,1,5-diazo naphthoquinone SULPHURYL CHLORIDE 40.5g(0.15mol), stirring is warming up to about 40 ℃, extremely reaction becomes orange red transparent, keep 40～45 ℃ and stir half an hour, splash into 10% sodium carbonate solution, it is principle that rate of addition is no more than 7 with the system pH value, do not descend to pH, when adding the theoretical amount of the hydrochloric acid that alkali number to neutralization reaction system produces, stop to add alkali, about 40 ℃, keep half an hour to 1 hour.About 3～4 hours of total reaction time.Be cooled to room temperature, reactant is injected 20 times deionized water, fully stir washing half an hour to 1 hour, decompress filter, washing, suction filtration is to taking out till not water outlet divides again.Dry 4 hours of 40 ℃ blast dry ovens, moved into vacuum drying oven drier 4 hours, product 68.5g, productive rate is 81%.Product dissolves in acetone, butanone, pimelinketone, dioxane, dimethyl formamide, ethylene glycol monoemethyl ether, the ethylene glycol monomethyl ether equal solvent.Infrared spectra and ultimate analysis proof have obtained expection product (III-1).

Synthesis example 12-15

With the method for synthesis example 11, the material of pressing table 1 with intermediate (I-2), (I-3), (I-4), (I-5) respectively can get end product (III-2)-(III-5) than replacing (I-1).

Table 1

Synthesis example 16

Separate without washing with synthesis example 6 gained reaction solns, directly add acetone 3500ml, 2,1,5-diazo naphthoquinone SULPHURYL CHLORIDE 405g(1.5mol, suitable phenolic hydroxyl group 50% import volume), stirring is warming up to 40 ℃, and is orange red transparent to reaction system, begins to drip 10% sodium carbonate solution after keeping half an hour at 40 ℃, the control rate of addition makes system pH between 6-7, and sodium carbonate amount is about the 1.3mol(2.6 equivalent).About 2 hours of dropping time.Dropwise at 40 ℃ and continue reaction 1 hour.Method washing with example 11 separates, drying, and surveying productive rate is 73%.Product is the orange/yellow solid powder, dissolves in soluble all kinds of SOLVENTS of example 11 products and the N-BUTYL ACETATE.Infrared spectroscopy shows, 3350cm ^-1Hydroxyl absorb and significantly to reduce 2120cm ^-1The diazonium quinonyl 1710cm significantly appears ^-1Carbonyl absorption and 1600cm ^-1Phenyl ring inhale to have all and have, illustrate to generate and expects product.

With import 0.75,1.0,1.5,1.8,2.0,2.5 respectively with quadrat method, 3.0mol 2,1,5-diazo naphthoquinone SULPHURYL CHLORIDE is made comparisons, import mole number little person's productive rate height (＞80%), but alkali-resistivity is poor, imports mole number＞2.0, the developing performance extreme difference, dirty serious on the bottom, productive rate is also low.Wherein import 1.5mol(phenolic hydroxyl group 50% importing rate) time, over-all properties is better.Product code name (III-6).

Synthesis example 17-20

Method with synthesis example 16 is described replaces (II-1) respectively with intermediate (II-2)-(II-5), adds alkali number and will consider that neutralization produces hydrogenchloride and acetic acid amount.Intermediate and 2,1, the feed ratio such as the table 2 of 5-diazo naphthoquinone SULPHURYL CHLORIDE are listed.

Table 2

Synthesis example 21

With synthesis example 1 gained reaction solution (1mol), add 74g Tetra hydro Phthalic anhydride (0.5mol), 100～110 ℃ of reactions 4 hours, can get the another complex ester of intermediate (II).And then with the method for synthesis example 16 synthetic product (III-11).

Use same quadrat method, after the Tetra hydro Phthalic anhydride of getting different ratios (0.1-0.8) adds, can get the product of different importing rates.

The method of use-case 21 is got acid anhydrides such as Tetra Hydro Phthalic Anhydride, chlordene Tetra hydro Phthalic anhydride, maleated rosin and is replaced Tetra hydro Phthalic anhydride, can obtain corresponding complex ester.And then can get a series of diazonium naphthoquinone sulphonates.

Embodiment 1

Synthesis example 16 products obtained therefroms are made into 5 kinds of sensitization liquid according to the ratio of components of table 3 sensitization coating fluid, go up coating about centrifugal coating 2 μ at the anodised aluminium sheet of a facing sand Mao Bingjing (PS version aluminium base) respectively, survey relative sensitivity or minimum decomposition light quantity with the Kodak-No221 section ash step-wedge of Kodak then, separate picture rule with little western six sites and survey resolving power (resolving power), receive the developing solution of-0.3% sodium hydroxide with 3% phosphoric acid and survey its alkali-resistivity and developing property, the results are shown in table 4.

The code name and the composition of table 3 sensitization coating fluid

Embodiment 2

With S-2 sensitization liquid after filter the decontamination chamber, be applied to the coating about 1 μ on the Al metallizing Fool that cleaned, separate picture rule with the mask of 1-5 micron at 80 ℃ of temperature preliminary dryings after 30 minutes and carried out the vacuum contact exposure 1 minute, with the developing liquid developing of embodiment 1 after 1 minute table 4 sensitization coating fluid S-1-S-5 as PS version photosensitive composition performance

With 1% salt acid rinse 10 seconds, washing and drying dried by the fire half an hour after 100 ℃, corrode in 70-80 ℃ strong phosphoric acid, can obtain clear etching pattern.Resist image resolving power 2-3 μ after developing, image resolving power 5 μ of aluminium film after the etching it serves to show that it has good antiacid erosion performance and high resolution.

Claims (7)

1, polyhutadiene is a positive light sensitivity Polymer Synthesizing method, and the structure of this based compound [III] is:

n+m=15-45

n/m=2-4，

It is characterized in that:

1.1 with weight-average molecular weight 1000～3000,1 of oxirane value 0.3-0.6,2-polyhutadiene epoxy and gallic acid are at catalyst n, under the effect of N--dimethyl benzylamine, with 1, the 4-dioxane is a solvent, and temperature of reaction is controlled at 100～130 ℃, and obtains the polyhutadiene gallic acid ester of following structure [I]:

N, m value are with [III] in the formula

1.2 with the esterification of polyhutadiene gallic acid, obtain the compound carboxylate of following structure [II] with the anhydrides compound:

N, m value same [III] in the formula,

To obtain polyhutadiene under the HCl agent effect be positive light sensitivity polymer [III] 1.3 take off in alkalescence with the diazo naphthoquinone SULPHURYL CHLORIDE of different ratios respectively with top two step products therefroms [I], [II].

2, be positive light sensitivity Polymer Synthesizing method according to the described polyhutadiene of claim 1, select weight-average molecular weight 1000～1500 when it is characterized in that synthetic mesophase product (I) for use, 1 of oxirane value 0.4～0.5,2-polyhutadiene epoxy with the identical or close gallic acid of epoxy group mole number.

3, be positive light sensitivity Polymer Synthesizing method according to claim 1 or 2 described polyhutadiene, the anhydrides compound is selected for use with epoxy and is rolled into a ball equimolar acetic anhydride when it is characterized in that synthetic mesophase product (II), and esterification temperature is 40～80 ℃.

4, be positive light sensitivity Polymer Synthesizing method according to claim 1 or 2 described polyhutadiene, when it is characterized in that synthesizing end product (III), select for use fusing point more than 125 ℃, especially 130～132 ℃ pure product 2,1,5-diazo naphthoquinone SULPHURYL CHLORIDE, its importing rate is controlled between 1/3～1/2.

5, be positive light sensitivity Polymer Synthesizing method according to the described polyhutadiene of claim 3, select for use fusing point more than 125 ℃ when it is characterized in that synthesizing end product (III), especially 130～132 ℃ pure product 2,1,5-diazo naphthoquinone SULPHURYL CHLORIDE, its importing rate is controlled between 1/3～1/2.

6, a kind of eurymeric resist of being made up of photosensitive polymer, bonding polymer and organic solvent is characterized in that containing (weight ratio):

1 polyhutadiene is that positive light sensitivity polymer (III) is as photosensitive polymer

1-3 meta-cresol resol is as the bonding polymer.

The 18-36 ethylene glycol monoemethyl ether is as solvent.

7,, it is characterized in that its best form (weight ratio) is according to the described eurymeric anti-corrosion additive of claim 6:

1 polyhutadiene is positive light sensitivity polymer (III)

1.5-2.5 meta-cresol resol

22.5-31.5 ethylene glycol monoemethyl ether.