POLY-P-HYDROXYSTYRENE EPOXY RESINS, SYNTHESIS AND APPLICATION THEREOF

Abstract

The present invention relates to a polymer of formula (I), wherein R.sub.a-R.sub.d, R.sub.a0-R.sub.d0, R.sub.a1-R.sub.d1, R.sub.a2-R.sub.d2, n, n.sub.0, n.sub.1 and n.sub.2 are as defined in the specification. When used as a film-forming resin for a photoresist, the polymer has such advantages as good ultraviolet light transmittance, high viscosity to form a thick film, fast photospeed, and high resolution. The present invention further relates to a process for the preparation of a polymer of formula (I), a use of a polymer of formula (I) as a film-forming resin in a photoresist, and a photoresist comprising a polymer of formula (I) as a film-forming resin.

##STR00001##

Claims

1. A polymer of formula (I) ##STR00008## wherein: each of R.sub.a-R.sub.d, each of R.sub.a0-R.sub.a0, each of R.sub.a1-R.sub.d1, and each of R.sub.a2-R.sub.d2 are respectively independently selected from the group consisting of H, halogen, C.sub.1-C.sub.6 alkyl, halo C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, halo C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.12 cycloalkyl and halo C.sub.3-C.sub.12 cycloalkyl; n and n.sub.0 are each independently a number from 0 to 40, and n+n.sub.0 is a number from 20 to 40; and n.sub.1 and n.sub.2 are each independently a number from 0 to 5.

2. The polymer according to claim 1, wherein each of R.sub.a-R.sub.d, each of R.sub.a0-R.sub.a0, each of R.sub.a1-R.sub.a1, and each of R.sub.a2-R.sub.d2 are respectively independently selected from H, chloro, bromo, C.sub.1-C.sub.4 alkyl, chloro C.sub.1-C.sub.4 alkyl, bromo C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, chloro alkoxy and bromo C.sub.1-C.sub.4 alkoxy; preferably, R.sub.a-R.sub.d, R.sub.a0-R.sub.d0, R.sub.a1-R.sub.d1, and R.sub.a2-R.sub.d2 are all H.

3. The compound according to claim 1 or 2, wherein n and n.sub.0 are each independently usually a number from 0 to 40, preferably a number from 0 to 20, more preferably a number from 12 to 18, and n+n.sub.0 is a number from 20 to 40, preferably a number from 24 to 36, more preferably a number from 25 to 30.

4. The polymer according to any one of claims 1 to 3, wherein n.sub.1 and n.sub.2 are each independently a number from 0 to 5, preferably a number from 0 to 2, more preferably 0; and/or n.sub.1+n.sub.2 is a number from 0 to 5, preferably a number from 0 to 3, and more preferably 0.

5. A process for the preparation of a polymer of formula (I) according to any one of claims 1 to 4, which comprises reacting a polymer of formula (II) with a compound of formula (III), ##STR00009## wherein n=n+n.sub.0+n.sub.1+n.sub.2, R.sup.a-R.sub.d, n, n.sub.0, n.sub.1 and n.sub.2 are each as defined in any one of claims 1 to 4, and X is a halogen, preferably chlorine or bromine.

6. The process according to claim 5, wherein the reaction of the polymer of formula (II) with the compound of formula (III) is carried out in the presence of an alkaline catalyst, which is preferably one or more selected from the group consisting of NaOH, KOH, Na.sub.2CO.sub.3, K.sub.2CO.sub.3, more preferably K.sub.2CO.sub.3.

7. The process according to claim 5 or 6, wherein the polymer of formula (II) and the compound of formula (III) are used in an amount such that the molar ratio of the monomer unit contained in the polymer of formula (II) to the compound of formula (III) is from 1:1 to 1:3, preferably from 1:1.8 to 1:2.0.

8. The process according to any one of claims 5 to 7, wherein the polymer of formula (II) and the alkaline catalyst are used in an amount such that the molar ratio of the monomer unit contained in the polymer of formula (II) to the alkaline catalyst is from 1:0.1 to 1:1, preferably from 1:0.6 to 1:1.

9. The process according to any one of claims 5 to 8, wherein the reaction of the polymer of formula (II) with the compound of formula (III) is carried out at 0-30 C., preferably at 25-30 C.

10. Use of a polymer of formula (I) according to any one of claims 1 to 4 as a film-forming resin in a photoresist.

11. A photoresist comprising the polymer of formula (I) according to any one of claims 1 to 4 as a film-forming resin.

12. The photoresist according to claim 11, which comprises the polymer of formula (I) according to any one of claims 1 to 4 as a film-forming resin, a photoacid generator, a photopolymerizable monomer, an alkaline additive, a sensitizer and a photoresist solvent; preferably, the mass ratio of the film-forming resin, photoacid generator, photopolymerizable monomer, alkaline additive, sensitizer, and photoresist solvent is (30-40): (1-4): (20-25): (1-2): (0-2): (40-50); more preferably, the mass ratio of the film-forming resin, photoacid generator, photopolymerizable monomer, alkaline additive, sensitizer, and photoresist solvent is 35:3.0:25:1.5:1.5:50.

13. The photoresist according to claim 12, wherein the photoacid generator is any one or more of an iodonium salt, a sulfonium salt, and a heterocyclic acid generator; preferably the iodonium salt, sulfonium salt and heterocyclic acid generators are respectively of the formulae (IV), (V) and (VI): ##STR00010## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are each independently phenyl, halophenyl, nitrophenyl, C.sub.6-C.sub.10 aryl or C.sub.1-C.sub.10 alkyl substituted benzoyl; and Y, Z are non-nucleophilic anions such as triflate, BF.sub.4.sup., ClO.sub.4.sup., PF.sub.6.sup., AsF.sub.6.sup. or SbF.sub.6.sup..

14. The photoresist according to claim 12 or 13, wherein the photopolymerizable monomer is N-vinylpyrrolidone, hydroxyethyl methacrylate or a mixture thereof; and/or the alkaline additive is a tertiary amine and/or a quaternary amine, more preferably any one or more of triethanolamine, trioctylamine and tributylamine; and/or the sensitizer is any one or more of 2,4-diethylthioxanthone, 9-anthracene methanol and 1-[(2,4-dimethylphenyl)azo]-2-naphthol; and/or the photoresist solvent is any one or more of cyclopcntanonc, -butyrolactone, and ethyl acetate.

Description

DESCRIPTION OF FIGURES

[0046] FIG. 1 is a lithographic image of the four photoresists obtained in Example 9; and

[0047] FIG. 2 is a lithographic image of the four photoresists obtained in Example 10.

MODE OF CARRYING OUT THE INVENTION

[0048] According to one aspect of the present invention, there is provided a polymer of the following formula (I):

##STR00005## [0049] wherein: [0050] each of R.sub.a-R.sub.d, each of R.sub.a0-R.sub.d0, each of R.sub.a1-R.sub.d1, and each of R.sub.a2-R.sub.d2 are respectively independently selected from the group consisting of H, halogen, C.sub.1-C.sub.6 alkyl, halo C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, halo C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.12 cycloalkyl and halo C.sub.3-C.sub.12 cycloalkyl; [0051] n and n.sub.0 are each independently a number from 0 to 40, and n+n.sub.0 is a number from 20 to 40; and [0052] n.sub.1 and n.sub.2 are each independently a number from 0 to 5.

[0053] In the present invention, R.sub.a-R.sub.d, R.sub.a0-R.sub.d0, R.sub.a1-R.sub.d1 and R.sub.a2-R.sub.d2 are groups on the benzene ring. R.sub.a-R.sub.d are the same or different, R.sub.a0-R.sub.d0 are the same or different, R.sub.a1-R.sub.D1 are the same or different, and R.sub.a2-R.sub.d2 are the same or different, and are each independently selected from H, halogen, C.sub.1-C.sub.6 alkyl, halo C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, halo C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.12 cycloalkyl and halo C.sub.3-C.sub.12 cycloalkyl. Preferably, each of R.sub.a-R.sub.d, each of R.sub.a0-R.sub.d0, each of R.sub.a1-R.sub.d1, and each of R.sub.a2-R.sub.d2 are respectively independently selected from H, chloro, bromo, C.sub.1-C.sub.4 alkyl, chloro C.sub.1-C.sub.4 alkyl, bromo C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, chloro C.sub.1-C.sub.4 alkoxy and bromo C.sub.1-C.sub.4 alkoxy. More preferably, R.sub.a-R.sub.d, R.sub.a0-R.sub.d0, R.sub.a1-R.sub.d1, and R.sub.a2-R.sub.d2 are all H. In addition, R.sub.a, R.sub.a0, R.sub.a1 and R.sub.a2 may be the same or different, preferably the same. R.sub.b, R.sub.b0, R.sub.b1 and R.sub.b2 may be the same or different, preferably the same. R.sub.c, R.sub.c0, R.sub.c1 and R.sub.c2 may be the same or different, preferably the same. R.sub.d, R.sub.d0, R.sub.d1, and R.sub.d2 may be the same or different, preferably the same.

[0054] In the present invention, n, n.sub.0, n.sub.1 and n.sub.2 each independently represent the number of structural units in the poly-p-hydroxystyrene epoxy resin. n and n.sub.0 are each independently a number from 0 to 40, preferably a number from 0 to 20, more preferably a number from 12 to 18. n+n.sub.0 is usually a number from 20 to 40, preferably a number from 24 to 36, more preferably a number from 25 to 30. n.sub.1 and n.sub.2 are each independently a number from 0 to 5, preferably a number from 0 to 2, more preferably 0. n.sub.1+n.sub.2 is usually a number from 0 to 5, preferably a number from 0 to 3, more preferably 0.

[0055] According to another aspect of the present invention, there is also provided a process for the preparation of a polymer of the formula (I) according to the present invention, which comprises reacting a polymer of formula (II) with a compound of formula (III),

##STR00006##

wherein n=n+n.sub.0+n.sub.1+n.sub.2, R.sub.a-R.sub.d, n, n.sub.0, n.sub.1 and n.sub.2 are each as defined for the polymer of formula (I), and X is a halogen, preferably chlorine or bromine.

[0056] In the present invention, the reaction of the polymer of formula (II) with the compound of formula (III) is usually carried out in the presence of an alkaline catalyst. There is no particular limitation on the selection of the alkaline catalyst. Preferably, the alkaline catalyst is one or more of NaOH, KOH, Na.sub.2CO.sub.3, K.sub.2CO.sub.3. More preferably, the alkaline catalyst is K.sub.2CO.sub.3. In the present invention, the reaction of the polymer of formula (II) with the compound of formula (III) is not particularly limited with respect to the amount of the alkaline catalyst. Preferably, the polymer of formula (II) and the alkaline catalyst are used in an amount such that the molar ratio of the monomer unit contained in the polymer of formula (II) to the alkaline catalyst is from 1:0.1 to 1:1. More preferably, the polymer of formula (II) and the alkaline catalyst are used in an amount such that the molar ratio of the monomer unit contained in the polymer of formula (Ti) to the alkaline catalyst is from 1:0.6 to 1:1.

[0057] In the present invention, the reaction of the polymer of formula (II) with the compound of formula (III) shall generally ensure that the polymer of formula (II) is thoroughly reacted. Thus, the polymer of formula (II) and the compound of formula (III) are used in an amount such that the molar ratio of the monomer unit contained in the polymer of formula (II) to the compound of formula (III) is from 1:1 to 1:3. Preferably, the polymer of formula (II) and the compound of formula (III) are used in an amount such that the molar ratio of the monomer unit contained in the polymer of formula (II) to the compound of formula (III) is from 1:1.8 to 1:2.0.

[0058] In the present invention, the reaction of the polymer of formula (II) with the compound of formula (III) is usually carried out in a solution. There is no particular limitation on the selection of the solvent as long as each reactant can be dissolved. Advantageously, the reaction of the polymer of formula (II) with the compound of formula (III) is carried out in the presence of an organic solvent. Preferably, the organic solvent is one or more selected from the group consisting of ethanol, acetone, ethyl acetate, dichloromethane, and trichloromethane. More preferably, the organic solvent is one selected from the group consisting of ethanol and acetone.

[0059] In the present invention, the reaction conditions such as temperature and pressure required for the reaction of the polymer of formula (II) with the compound of formula (III) are conventional. Preferably, the reaction is carried out at 0-30 C. More preferably, the reaction is carried out at 25-30 C. The reaction time is advantageously from 8 to 10 hours. The reaction pressure is advantageously atmospheric.

[0060] The product prepared is subjected to infrared characterization to observe whether the hydroxyl peaks in the vicinity of 3500 cm.sup.1 in the infrared spectrum are weakened or even disappeared or whether there is introduction of epoxy groups, thereby judging whether the polymer of formula (I) according to the present invention is obtained, and the structure of the product is confirmed by .sup.1H-NMR.

[0061] By way of example, the preparation of a polymer of formula (I) by the reaction of a polymer of formula (II) with a compound of formula (III) can generally be carried out as follows:

[0062] Step 1): a polymer of formula (II) is mixed with an alkaline catalyst in a solvent to obtain a mixture;

[0063] Step 2): a compound of formula (III) is slowly added dropwise to the mixture obtained in Step 1) for reaction; and

[0064] Step 3): after completion of the reaction, it is filtered, the solvent and excess reactant are distilled off under reduced pressure to give a solid, which is washed, filtered, and dried to give a polymer of formula (I).

[0065] The operation of Step 1) can be carried out as follows: a polymer of formula (II) is first added into a solvent, stirred, nitrogen gas is introduced, and then an alkaline catalyst is added to obtain a mixture.

[0066] The operation of Step 2) can be carried out as follows: a compound of formula (III) is slowly added dropwise at 25-30 C. to the mixture obtained in Step 1), and the reaction is carried out for 8-10 hours.

[0067] The operation of Step 3) can be carried out as follows: after completion of the reaction, the undissolved alkaline catalyst and the produced inorganic salt are removed by filtration, the filtrate is distilled under reduced pressure, the solvent and the excess compound of formula (III) are distilled off to obtain a solid, which is washed with water, filtered, and dried to obtain a polymer of formula (I).

[0068] According to still another aspect of the present invention, there is provided the use of a polymer of formula (I) according to the present invention as a film-forming resin in a photoresist. When the polymer of formula (I) according to the present invention is used as a film-forming resin for a photoresist, with poly-p-hydroxystyrene as the main structure, said polypara-hydroxystyrene itself is synthesized by a polyaddition reaction, a resin with high molecular weight and narrow molecular weight distribution can be obtained by a cation controlled active polymerization, and poly-p-hydroxystyrene also has a good ultraviolet light transmission. Said characteristics as high molecular weight, narrow molecular weight distribution, good ultraviolet light transmittance are all conducive to improving the resolution of photoresists. There are a large amount of benzene rings in the resin structure, and the rigidity of benzene rings allows the resin to have good anti-etching property. The epoxy group introduced into the resin can undergo cationic photopolymerization, the photospeed is fast and there is no oxygen inhibition, thus the polymerization reaction is not easily terminated, can be continued even in the dark, and a crosslinked network is easily formed in the exposed region, thereby obtaining a high resolution lithographic image. Another advantage of epoxy resin is the high viscosity, so the photoresist film obtained has good adhesion to the substrate, and a thick photoresist film can be obtained.

[0069] According to the final aspect of the present invention, there is provided a photoresist comprising the polymer of formula (I) according to the present invention as a film-forming resin.

[0070] In general, the photoresist of the present invention consists substantially of the following components: a polymer of formula (I) as a film-forming resin, a photoacid generator, a photopolymerizable monomer, an alkaline additive, a sensitizer and a photoresist solvent. Preferably, the mass ratio of the film-forming resin, photoacid generator, photopolymerizable monomer, alkaline additive, sensitizer, and photoresist solvent is (30-40): (1-4): (20-25): (1-2): (0-2): (40-50). More preferably, the mass ratio of the film-forming resin, photoacid generator, photopolymerizable monomer, alkaline additive, sensitizer, and photoresist solvent is 35:3.0:25:1.5:1.5:50. By substantially herein is meant that at least 90% by weight, more preferably at least 95% by weight, especially at least 98% by weight, in particular at least 99% by weight, of the total weight of the photoresist is composed of a polymer of formula (I) as a film-forming resin, a photoacid generator, a photopolymerizable monomer, an alkaline additive, a sensitizer and a photoresist solvent.

[0071] In the present invention, the photoresist film-forming resin is any one or more of the polymers of formula (I).

[0072] It is preferred according to the present invention that the photoacid generator is any one or more of an iodonium salt, a sulfonium salt, and a heterocyclic acid generator. Advantageously, the iodonium salt, sulfonium salt and heterocyclic acid generators are respectively of the formulae (IV), (V) and (VI):

##STR00007##

wherein
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are each independently phenyl, halophenyl, nitrophenyl, C.sub.6-C.sub.10 aryl or C.sub.1-C.sub.10 alkyl substituted benzoyl; and
Y, Z are non-nucleophilic anions such as triflate, BF.sub.4.sup., ClO.sub.4.sup., PF.sub.6.sup., AsF.sub.6.sup. or SbF.sub.6.sup..

[0073] It is preferred according to the present invention that the photopolymerizable monomer is N-vinylpyrrolidone, hydroxyethyl methacrylate or a mixture thereof

[0074] It is preferred according to the present invention that the alkaline additive is a tertiary amine and/or a quaternary amine, more preferably any one or more of triethanolamine, trioctylamine and tributylaminc.

[0075] It is preferred according to the present invention that the sensitizer is a sensitizer sensitive to a specific wavelength, e.g., any one or more of 2,4-diethylthioxanthone, 9-anthracene methanol and 1-[(2,4-dimethylphenyl)azo]-2-naphthol.

[0076] It is preferred according to the present invention that the photoresist solvent is any one or more of cyclopentanone, -butyrolactone, and ethyl acetate.

[0077] The polymer of formula (I) according to the present invention has the following beneficial effects as a film-forming resin of photoresists: with poly-p-hydroxystyrene as the main structure, said poly-p-hydroxystyrene itself is synthesized by a polyaddition reaction, a resin with high molecular weight and narrow molecular weight distribution can be obtained by a cation controlled active polymerization, and poly-p-hydroxystyrene also has a good ultraviolet light transmission. Said characteristics as high molecular weight, narrow molecular weight distribution, good ultraviolet light transmittance are all conducive to improving the resolution of photoresists. There are a large amount of benzene rings in the resin structure, and the rigidity of benzene rings allows the resin to have good anti-etching property. In particular, compared with other photoresist film-forming resins with poly-p-hydroxystyrene as the main structure, the film-forming resin of the present invention has introduced an epoxy group, which can undergo cationic photopolymerization, the photospeed is fast and there is no oxygen inhibition, thus the polymerization reaction is not easily terminated, can be continued even in the dark, and a crosslinked network is easily formed in the exposed region, thereby obtaining a high resolution lithographic image. Another advantage of epoxy resin is the high viscosity, so the photoresist film obtained has good adhesion to the substrate, and a thick photoresist film can be obtained.

EXAMPLES

[0078] The present invention is further illustrated by reference to the following examples, which should not be construed as having any limitation on the protection scope of the present invention.

[0079] The characterization and detection methods involved in the following examples are as follows:

1. Infrared Spectroscopy Characterization Method

[0080] The infrared spectrum was measured by IRAffinity Fourier Transform Infrared Spectrometer, Shimadzu Corporation, with a scanning range of 4000-400 cm.sup.1, and the sample was processed by a KBr tableting method.

2. .SUP.1.H NMR Spectrum Characterization Method

[0081] .sup.1H NMR was measured by a Bruker Avame PRX400 nuclear magnetic resonance apparatus, the chemical shift was expressed in ppm, the solvent was deuterated chloroform, the internal standard was tetramethylsilane, the scanning width was 400 MHz, and the number of scanning was 16 times.

3. Ultraviolet Absorption Spectrometry Method

[0082] Using acetonitrile as a solvent, the sample was formulated into a solution having a concentration of 30 ppm, and the ultraviolet absorption spectrum was measured by a Shimadzu UV-2450 ultraviolet-visible spectrophotometer. The measurement range was 200-400 nm, the resolution was 0.1 nm, the spectrum width was 0.1-5 nm, and the stray light as 0.015% or less.

4. Epoxy Value Determination Method

[0083] The epoxy value of the sample was measured by the hydrochloric acid-acetone method. 0.4 g of sample was accurately weighed and added to a 250 mL closed conical flask, after which 25 mL of 0.2 mol/L hydrochloric acid acetone solution was added, shaken to completely dissolve the sample, and after standing at room temperature for 2 h, 3 drops of phenolphthalein reagent were added, titrated with 0.1 mol/L sodium hydroxide-ethanol standard solution until the solution turned pink, and two blank titrations were carried out under the same conditions. The volume of the sodium hydroxide standard solution required for titration was recorded, and the epoxy value of the sample was calculated according to the formula (1).

In the formula:

[00001]$\begin{array}{cc}E=\frac{\left(V_1-V_2\right)c_{\mathrm{NaOil}}}{10.Math..Math.m}& \left(1\right)\end{array}$ [0084] Eepoxy value, mol/100 g; [0085] V1the volume of sodium hydroxide-ethanol standard solution consumed by the blank experiment, mL; [0086] V.sub.2the volume of sodium hydroxide-ethanol standard solution consumed by the sample, mL; [0087] c.sub.NaOHthe concentration of sodium hydroxide-ethanol standard solution, mol/L; [0088] mmass of the sample, g.

Example 1: Poly 4-(2,3-glycidoxy)styrene

[0089] 50 ml of acetone was selected as solvent, to which 12 g of poly-p-hydroxystyrene (number average molecular weight of 3000, n=25) (0.1 mol of repeating unit) was added, electrically stirred while introducing nitrogen, and 2.4 g (0.06 mol) of sodium hydroxide was added. The temperature of the reaction mixture obtained was controlled at 25 C., and 16.65 g of epichlorohydrin (0.18 mol) was slowly added dropwise through a constant pressure dropping funnel, and the dropwise addition was completed in 0.5 h, afterwards the resulting reaction mixture was reacted at 25 C. for 8 h. After completion of the reaction, the undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure, the solvent and the excess epichlorohydrin were distilled off to obtain a solid, which was washed three times with water, filtered, and dried to obtain a product, which was shown to be the title polymer according to analysis.

[0090] The nuclear magnetic data are as follows (d-CDCl.sub.3): methylene of the polystyrene chain was at 1.87; methylene of the epoxy ring was at 2.50; methine of the polystyrene chain was at 2.76; H of the benzene ring was at 6.69, 7.02; methylene of the glycidoxy group attached to oxygen was at 4.07; methine of the epoxy ring was at 3.04, and no hydroxyl signal was detected.

[0091] Infrared spectroscopy results: no hydroxyl stretching vibration peak was detected at 3100 cm.sup.1-3500 cm.sup.1, and a characteristic absorption peak of the epoxy ring was detected at 910 cm.sup.1.

[0092] Ultraviolet absorption spectrum results: the maximum absorption wavelength was 226 nm, with no ultraviolet absorption peak above 226 nm, and there was good light transmission in the ultraviolet light region above 226 nm.

[0093] Epoxy value measurement result: the epoxy value was 0.57 mol/100 g.

Example 2: Poly 3,5-dimethyl-4-(2,3-glycidoxy)styrene

[0094] 50 ml of ethanol was selected as solvent, to which 14.8 g of poly 3,5-dimethyl-4-hydroxystyrene (number average molecular weight of 2960, n=20) (0.1 mol of repeating unit) was added, electrically stirred while introducing nitrogen, and 5.6 g (0.1 mol) of potassium hydroxide was added. The temperature of the reaction mixture obtained was controlled at 20 C., and 18.5 g of epichlorohydrin (0.2 mol) was slowly added dropwise through a constant pressure dropping funnel, and the dropwise addition was completed in 0.5 h, afterwards the resulting reaction mixture was reacted at 25 C. for 8 h. After completion of the reaction, the undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure, the solvent and the excess epichlorohydrin were distilled off to obtain a solid, which was washed three times with water, filtered, and dried to obtain a product, which was shown to be the title polymer according to analysis.

[0095] The nuclear magnetic data are as follows (d-CDCl.sub.3): methylene of the polystyrene chain was at 1.87; methyl was at 2.34, methylene of the epoxy ring was at 2.50; methine of the polystyrene chain was at 2.76; H of the benzene ring was at 6.63; methylene of the glycidoxy group attached to oxygen was at 4.07; methine of the epoxy ring was at 3.04, and no hydroxyl signal was detected.

[0096] Infrared spectroscopy results: no hydroxyl stretching vibration peak was detected at 3100 cm.sup.1-3500 cm.sup.1, and a characteristic absorption peak of the epoxy ring was detected at 911 cm.sup.1.

[0097] Ultraviolet absorption spectrum results: the maximum absorption wavelength was 219 nm, with no ultraviolet absorption peak above 219 nm, and there was good light transmission in the ultraviolet light region above 219 nm.

[0098] Epoxy value measurement result: the epoxy value was 0.49 mol/100 g.

Example 3: Poly 3-ethoxy-4-(2,3-glycidoxy)styrene

[0099] 50 ml of ethyl acetate was selected as solvent, to which 16.4 g of poly 3-ethoxy-4-hydroxystyrene (number average molecular weight of 4920, n=30) (0.1 mol of repeating unit) was added, electrically stirred while introducing nitrogen, and 8.28 g (0.06 mol) of potassium carbonate was added. The temperature of the reaction mixture obtained was controlled at 30 C., and 18.5 g of epichlorohydrin (0.2 mol) was slowly added dropwise through a constant pressure dropping funnel, and the dropwise addition was completed in 0.5 h, afterwards the resulting reaction mixture was reacted at 25 C. for 10 h. After completion of the reaction, the undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure, the solvent and the excess epichlorohydrin were distilled off to obtain a solid, which was washed three times with water, filtered, and dried to obtain a product, which was shown to be the title polymer according to analysis.

[0100] The nuclear magnetic data are as follows (d-CDCl.sub.3): methylene of the polystyrene chain was at 1.87; methyl was at 1.33, methylene of the ethoxy group was at 3.98; methylene of the epoxy ring was at 2.50; methine of the polystyrene chain was at 2.76; H of the benzene ring was at 6.58, 6.53; methylene of the glycidoxy group attached to oxygen was at 4.07; methine of the epoxy ring was at 3.04, and no hydroxyl signal was detected.

[0101] Infrared spectroscopy results: no hydroxyl stretching vibration peak was detected at 3100 cm.sup.1-3500 cm.sup.1, and a characteristic absorption peak of the epoxy ring was detected at 914 cm.sup.1.

[0102] Ultraviolet absorption spectrum results: the maximum absorption wavelength was 223 nm, with no ultraviolet absorption peak above 223 nm, and there was good light transmission in the ultraviolet light region above 223 nm.

[0103] Epoxy value measurement result: the epoxy value was 0.45 mol/100 g.

Example 4: Poly 2-chloro-4-(2,3-glycidoxy)styrene

[0104] 50 ml of ethyl acetate was selected as solvent, to which 15.5 g of poly 2-chloro-4-hydroxystyrene (number average molecular weight of 3887, n=25) (0.1 mol of repeating unit) was added, electrically stirred while introducing nitrogen, and 6.36 g (0.06 mol) of sodium carbonate was added. The temperature of the reaction mixture obtained was controlled at 30 C., and 16.65 g of epichlorohydrin (0.18 mol) was slowly added dropwise through a constant pressure dropping funnel, and the dropwise addition was completed in 0.5 h, afterwards the resulting reaction mixture was reacted at 30 C. for 9 h. After completion of the reaction, the undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure, the solvent and the excess epichlorohydrin were distilled off to obtain a solid, which was washed three times with water, filtered, and dried to obtain a product, which was shown to be the title polymer according to analysis.

[0105] The nuclear magnetic data are as follows (d-CDCl.sub.3): methylene of the polystyrene chain was at 1.87; methine of the polystyrene chain was at 2.76; H of the benzene ring was at .sup. 6.57, 6.70, 6.96; methylene of the glycidoxy group attached to oxygen was at 4.07; methine of the epoxy ring was at 3.04; methylene of the epoxy ring was at 2.50, and no hydroxyl signal was detected.

[0106] Infrared spectroscopy results: no hydroxyl stretching vibration peak was detected at 3100 cm.sup.1-3500 cm.sup.1, and a characteristic absorption peak of the epoxy ring was detected at 914 cm.sup.1.

[0107] Ultraviolet absorption spectrum results: the maximum absorption wavelength was 217 mu, with no ultraviolet absorption peak above 217 nm, and there was good light transmission in the ultraviolet light region above 217 nm.

[0108] Epoxy value measurement result: the epoxy value was 0.47 mol/100 g.

Example 5: Poly 2-chloromethyl-4-(2,3-glycidoxy)styrene

[0109] 50 ml of dichloromethane was selected as solvent, to which 17 g of poly 2-chloromethyl-4-hydroxystyrene (number average molecular weight of 5055, n=30) (0.1 mol of repeating unit) was added, electrically stirred while introducing nitrogen, and 2.4 g (0.06 mol) of sodium hydroxide was added. The temperature of the reaction mixture obtained was controlled at 30 C., and 16.65 g of epichlorohydrin (0.18 mol) was slowly added dropwise through a constant pressure dropping funnel, and the dropwise addition was completed in 0.5 h, afterwards the resulting reaction mixture was reacted at 25 C. for 8 h. After completion of the reaction, the undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure, the solvent and the excess epichlorohydrin were distilled off to obtain a solid, which was washed three times with water, filtered, and dried to obtain a product, which was shown to be the title polymer according to analysis.

[0110] The nuclear magnetic data are as follows (d-CDCl.sub.3): methylene of the polystyrene chain was at 1.87; methine of the polystyrene chain was at 2.76; H of the benzene ring was at 6.70, 7.02; methylene of the glycidoxy group attached to oxygen was at S4.07; methine of the epoxy ring was at 3.04; chloromethyl was at 4.64; methylene of the epoxy ring was at 2.50; and a weak hydroxyl peak was detected at 5.07.

[0111] Infrared spectroscopy results: a weak hydroxyl stretching vibration peak was detected at 3100 cm.sup.1-3500 cm.sup.1, and a characteristic absorption peak of the epoxy ring was detected at 914 cm.sup.1.

[0112] Ultraviolet absorption spectrum results: the maximum absorption wavelength was 224 nm, with no ultraviolet absorption peak above 224 mu, and there was good light transmission in the ultraviolet light region above 224 nm.

[0113] Epoxy value measurement result: the epoxy value was 0.40 mol/100 g.

Example 6: Poly 2-methyl-5-methoxy-4-(2,3-glycidoxy)styrene

[0114] ml of acetone was selected as solvent, to which 16.4 g of poly 2-methyl-5-methoxy-4-hydroxystyrene (number average molecular weight of 5740, n=35) (0.1 mol of repeating unit) was added, electrically stirred while introducing nitrogen, and 11.04 g (0.08 mol) of potassium carbonate was added. The temperature of the reaction mixture obtained was controlled at 30 C., and 17.58 g of epichlorohydrin (0.19 mol) was slowly added dropwise through a constant pressure dropping funnel, and the dropwise addition was completed in 0.5 h, afterwards the resulting reaction mixture was reacted at 25 C. for 8 h. After completion of the reaction, the undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure, the solvent and the excess epichlorohydrin were distilled off to obtain a solid, which was washed three times with water, filtered, and dried to obtain a product, which was shown to be the title polymer according to analysis.

[0115] The nuclear magnetic data are as follows (d-CDCl.sub.3): methylene of the polystyrene chain was at 1.87; methine of the polystyrene chain was at 2.76; H of the benzene ring was at 6.38, 6.41; methylene of the glycidoxy group attached to oxygen was at 4.07; methine of the epoxy ring was at 3.04; methyl was at 2.35; methoxy was at 3.73; methylene of the epoxy ring was at 2.50, and a weak hydroxyl peak was detected at 5.03.

[0116] Infrared spectroscopy results: a weak hydroxyl stretching vibration peak was detected at 3100 cm.sup.1-3500 cm.sup.1, and a characteristic absorption peak of the epoxy ring was detected at 910 cm.sup.1.

[0117] Ultraviolet absorption spectrum results: the maximum absorption wavelength was 218 nm, with no ultraviolet absorption peak above 218 nm, and there was good light transmission in the ultraviolet light region above 218 nm.

[0118] Epoxy value measurement result: the epoxy value was 0.40 mol/100 g.

Example 7: Poly 3-cyclopropyl-4-(2,3-glycidoxy)styrene

[0119] ml of acetone was selected as solvent, to which 16.1 g of poly 3-cyclopropyl-4-hydroxystyrene (number average molecular weight of 6440, n=40) (0.1 mol of repeating unit) was added, electrically stirred while introducing nitrogen, and 4.2 g (0.075 mol) of potassium hydroxide was added. The temperature of the reaction mixture obtained was controlled at 30 C., and 17.58 g of epichlorohydrin (0.19 mol) was slowly added dropwise through a constant pressure dropping funnel, and the dropwise addition was completed in 0.5 h, afterwards the resulting reaction mixture was reacted at 25 C. for 9 h. After completion of the reaction, the undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure, the solvent and the excess epichlorohydrin were distilled off to obtain a solid, which was washed three times with water, filtered, and dried to obtain a product, which was shown to be the title polymer according to analysis.

[0120] The nuclear magnetic data are as follows (d-CDCl.sub.3): methylene of the polystyrene chain was at 1.87; methine of the polystyrene chain was at 2.76; H of the benzene ring was at 6.89, 6.84, 6.61; methylene of the glycidoxy group attached to oxygen was at 4.07; methine of the epoxy ring was at 3.04; methylene of the epoxy ring was at 2.50, methine of the cyclopropyl group was at 1.51; methylene of the cyclopropyl group was at 0.51, and a very small hydroxyl peak was detected at 5.41.

[0121] Infrared spectroscopy results: a weak hydroxyl stretching vibration peak was detected at 3100 cm.sup.1-3500 cm.sup.1, and a characteristic absorption peak of the epoxy ring was detected at 912 cm.sup.1.

[0122] Ultraviolet absorption spectrum results: the maximum absorption wavelength was 226 nm, with no ultraviolet absorption peak above 226 nm, and there was good light transmission in the ultraviolet light region above 226 nm.

[0123] Epoxy value measurement result: the epoxy value was 0.42 mol/100 g.

Example 8: Poly 2-chloro-5-ethoxy-4-(2,3-glycidoxy)styrene

[0124] 50 ml of ethanol was selected as solvent, to which 19.85 g of poly 2-chloro-5-ethoxy-4-hydroxystyrene (number average molecular weight 6948, n=35) (0.1 mol of repeating unit) was added, electrically stirred while introducing nitrogen, and 8.48 g (0.08 mol) of sodium carbonate was added. The temperature of the reaction mixture obtained was controlled at 30 C., and 18.5 g of epichlorohydrin (0.2 mol) was slowly added dropwise through a constant pressure dropping funnel, and the dropwise addition was completed in 0.5 h, afterwards the resulting reaction mixture was reacted at 25 C. for 10 h. After completion of the reaction, the undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure, the solvent and the excess epichlorohydrin were distilled off to obtain a solid, which was washed three times with water, filtered, and dried to obtain a product, which was shown to be the title polymer according to analysis.

[0125] The nuclear magnetic data are as follows (d-CDCl.sub.3): methylene of the polystyrene chain was at 1.87; methine of the polystyrene chain was at 2.76; H of the benzene ring was at 6.47, 6.59; methylene of the glycidoxy group attached to oxygen was at 4.07; methine of the epoxy ring was at 3.04; methylene of the epoxy ring was at 2.50; methyl of the ethoxy group was at 1.33; methylene of the ethoxy group was at 3.98; and a weak hydroxyl peak was detected at 5.13.

[0126] Infrared spectroscopy results: a weak hydroxyl stretching vibration peak was detected at 3100 cm.sup.1-3500 cm.sup.1, and a characteristic absorption peak of the epoxy ring was detected at 909 cm.sup.1.

[0127] Ultraviolet absorption spectrum results: the maximum absorption wavelength was 220 nm, with no ultraviolet absorption peak above 220 nm, and there was good light transmission in the ultraviolet light region above 220 nm.

[0128] Epoxy value measurement result: the epoxy value was 0.37 mol/100 g.

Example 9

[0129] Four negative chemically amplified photoresists were prepared as follows: 30 g of each of the polymers prepared in Examples 1-4, 2 g of 3-nitrophenyl diphenylthio hexafluorophosphate, 25 g of N-vinylpyrrolidone, 1.8 g of trioctylamine, 1 g of 9-anthracene methanol and 50 g of ethyl acetate were respectively weighed, the above materials were mixed and thoroughly stirred to completely dissolve, and filtered through a 0.45 M polytetrafluoroethylene microporous filter membrane, thereby obtaining four new negative chemically amplified photoresists.

Example 10

[0130] Four negative chemically amplified photoresists were prepared as follows: 40 g of each of the polymers prepared in Examples 5-8, 3 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 20 g of hydroxyethyl methacrylate, 1.5 g of triethanolamine, 1.5 g of 2,4-diethylthioxanthone and 50 g of cyclopentanone were respectively weighed, the above materials were mixed and thoroughly stirred to completely dissolve, and filtered through a 0.45 m polytetrafluoroethylene microporous filter membrane, thereby obtaining four new negative chemically amplified photoresists.

Example 11

[0131] The four negative chemically amplified photoresists obtained in the above Example 9 were respectively coated on a 6-inch single crystal silicon wafer by spin coating (rotation speed: 4000 rpm), baked at 90 C. for 2 minutes, and cooled to room temperature, after which the coated silicon wafer was exposed in an exposure machine having a wavelength of 365 nm, baked at 110 C. for 2 minutes after exposure, and developed with a propylene glycol methyl ether acetate aqueous solution as a developing solution for 60 s to obtain a lithographic image. The lithographic images of the photoresists obtained by the polymers from Examples 1-4 are shown in FIGS. 1(a)-(d), respectively.

Example 12

[0132] The four negative chemically amplified photoresists obtained in the above Example 10 were respectively coated on a 6-inch single crystal silicon wafer by spin coating (rotation speed: 4000 rpm), baked at 100 C. for 2 minutes, and cooled to room temperature, after which the coated silicon wafer was exposed in an exposure machine having a wavelength of 248 nm, baked at 100 C. for 2 minutes after exposure, and developed with a propylene glycol methyl ether acetate aqueous solution as a developing solution for 50 s to obtain a lithographic image. The lithographic images of the photoresists obtained by the polymers from Examples 5-8 are shown in FIGS. 2(a)-(d), respectively.

[0133] As can be seen from FIG. 1, by using the polymers from Examples 1-4 as film-forming resins, the formulated photoresists are subjected to such procedure as exposure and development, thereby obtaining a clear image with a diameter of about 30 m, the image has a high resolution, regular pattern arrangement, complete edge, and no glue drop-off or residue phenomenon.

[0134] As can be seen from FIG. 2, by using the polymers from Examples 5-8 as film-forming resins, the formulated photoresists are subjected to such procedure as exposure and development, thereby obtaining thick photoresist films, the sidewall of the image is steep, the height is up to 70 m, and the aspect ratio may be up to 1:1.

[0135] The polymers prepared in the above Examples are used for negative chemically amplified photoresists. Based on the cationic photocuring of epoxy groups, a chemical amplification technology is adopted, and with polyhydroxystyrene as the main structure, such characteristics as high molecular weight, narrow molecular weight distribution, good ultraviolet light transmittance allow the photoresists to have a favorable resolution. The introduction of the epoxy structure makes it possible for the resin to easily form a crosslinked network in the exposed area, thereby obtaining a high-resolution lithographic image; in addition, the high viscosity of the epoxy resin allows the obtained photoresist film to have good adhesion to the substrate, so that a thick photoresist film can be easily obtained, and after its exposure and development, a clear image with a diameter of 30 m and a thickness of up to 70 m can be easily obtained, thus having a bright application prospect in the field of thick-film photoresists.