KR19990000269A - Method for producing polyhydroxy styrene derivative - Google Patents

Abstract

The present invention provides a polyhydroxystyrene derivative comprising adding polyhydroxystyrene to an alkaline alcohol solution to form a uniform polyhydroxystyrene solution, and reacting the polyhydroxystyrene solution with an ester to obtain a polyhydroxystyrene derivative. It provides a manufacturing method. The obtained polyhydroxystyrene derivative is suitable for use as the resin component of the photoresist.

Description

Method for producing polyhydroxy styrene derivative

The present invention relates to a method for producing a polyhydroxystyrene derivative, and more particularly, to a polyhydroxystyrene derivative using an alkaline alcohol solution as a solvent for dissolving polyhydroxystyrene in order to allow the polyhydroxystyrene and the ester to react in a homogeneous system. It relates to a method for producing.

Representative photoresist compositions include resins, photoacid generators, inhibitors and other additives. An ideal photoresist composition should satisfy the requirements of excellent resolution, photosensitivity, etch resistance, adhesion, thermal stability, film homogeneity and processability. Since the resin is the main component in the photoresist, the resin has a significant influence on the above-described properties, and is particularly a key factor in improving the etching resistance, adhesion performance and film homogeneity performance.

Generally speaking, polyhydroxystyrene copolymers have low absorption and excellent thermal stability at a wavelength of 248 nm, so they are often used as the resin component of the photoresist. In general, there are two ways to prepare copolymers (or derivatives) of polyhydroxystyrene. One is the direct polymerization of two different monomers. For example, US Pat. No. 4,775,730 describes the direct polymerization of styrene derivatives with another alkene derivatives, followed by continuous hydrolysis of the resulting copolymer to give the desired product. This reaction is shown in Scheme 1 below.

Scheme 1

However, J. J. Polym. Sci .: Part A; Polym. Chem. Ed. 1986, 24, 2971 describe the polymerization of two different styrene monomers followed by the selective degradation of functional groups. This reaction is shown in Scheme 2.

Scheme 2

Another method of preparing polyhydroxystyrene copolymers involves allowing the ester reagent and polyhydroxystyrene to react using polyhydroxystyrene as starting material. For example, European Patent No. 0634696 discloses dissolving polyhydroxystyrene in tetrahydrofuran (THF) followed by the addition of potassium t-butoxide [KOC (CH ₃ ) ₃ ] and then the mixture being di (t- React with butyl) dicarbonate to obtain polyhydroxystyrene derivatives. However, under the above conditions, potassium salt of polyhydroxystyrene is not dissolved in THF. Thus, the continuous reaction of polyhydroxystyrene and di (t-butyl) dicarbonate is carried out in a heterogeneous system. The overall reaction is shown in Scheme 3 below.

Scheme 3

In summary, conventional methods of preparing polyhydroxystyrene derivatives include complex synthetic processes or are time consuming and the functionality of each polyhydroxystyrene molecule differs greatly because the reaction is carried out in a heterogeneous system, thus the product Quality is not easily adjusted.

It is therefore an object of the present invention to solve the above problems and to provide a method which is easy to prepare polyhydroxystyrene derivatives.

The present invention allows the reaction to be carried out in a uniform manner using a special solvent system, so that the starting material polyhydroxystyrene is completely dissolved in the reaction system, and the functionalities of the respective polyhydroxystyrene molecules are not significantly different from each other. This allows the quality of the product to be effectively controlled. In addition, the solvents used have very low toxicity, the reaction is carried out at room temperature, no heating and reflux or low temperature equipment is required for this kind of reaction. Thus, the reaction of the present invention is simpler, time-saving, safe and of high commercial value.

According to the present invention, a method for producing a polyhydroxystyrene derivative in order to achieve the above object

(a) polyhydroxystyrene is added to an alkaline alcohol solution, wherein the alkaline alcohol solution is obtained by mixing an alkali reagent and an alcohol to form a homogeneous polyhydroxystyrene solution,

(b) reacting the polyhydroxystyrene solution with an ester of the formula (1) to obtain a polyhydroxystyrene derivative.

[Formula 1]

Where

R ₁ is F, Cl, Br and Wherein R ₃ is a hydrocarbon group having 1 to 8 carbon atoms,

R ₂ is a hydrocarbon group having 1 to 8 carbon atoms.

According to the present invention, the starting material used to prepare the polyhydroxystyrene derivatives is commercially available polyhydroxystyrene. Polyhydroxystyrene is added to the alkaline alcohol solution and then thoroughly stirred to form a homogeneous polyhydroxystyrene solution. So-called alkaline alcohol solutions are obtained by mixing alkali reagents with alcohols. All alkali / alcohol mixtures capable of dissolving polyhydroxystyrene are suitable for use in the present invention.

The polyhydroxystyrene solution is then reacted with the ester for a predetermined time. Water is added to precipitate the product, followed by filtration and drying to give a polyhydroxystyrene derivative.

When the OH groups are functionalized in a certain proportion, the product can be precipitated using the alkali / alcohol solution system described above to synthesize the polyhydroxystyrene derivatives. Therefore, in order to obtain a polyhydroxystyrene derivative having a higher functionalization ratio, an organic solvent can be added after the reaction of the polyhydroxystyrene solution with the ester to dissolve the product, and the ester reagent is added again to obtain a suitable reactant. May be provided to further functionalize the unreacted OH groups of the polyhydroxystyrene. Thus, the degree of functionality of the final product can be increased. Suitable organic solvents include all kinds of solvents capable of dissolving polyhydroxystyrene derivatives. A representative example is N, N-dimethylformamide (DMF).

Suitable alkali reagents for use in the present invention are alkali metal compounds or base compounds comprising nitrogen atoms. The alkali metal compound may be a hydroxide or alkoxide of alkali metal. Representative examples include sodium hydroxide, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide and potassium t-butoxide.

Base compounds containing nitrogen atoms suitable for use in the present invention , , , , , , And It is selected from the group consisting of.

Wherein R ₄ , R ₅ , R ₆ are selected from the group consisting of H and a hydrocarbon group having 1 to 4 carbon atoms, and X is O or N. Representative examples of such nitrogen containing base compounds include trimethylamine and triethylamine.

Alcohols suitable for use in the present invention may be alcohols having 1 to 6 carbon atoms. Representative examples include methanol, ethanol and isopropanol.

Suitable ester reagents for use in the present invention include the structure shown by formula (1).

[Formula 1]

In the formula,

R ₁ is F, Cl, Br and Wherein R ₃ is a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group selected from the group consisting of alkyl, phenyl, benzyl, substituted alkyl, substituted phenyl and substituted benzyl having 1 to 8 carbon atoms. Selected from the group consisting of

R ₂ is a hydrocarbon group selected from the group consisting of a hydrocarbon group having 1 to 8 carbon atoms, preferably alkyl, phenyl, benzyl, substituted alkyl, substituted phenyl, and substituted benzyl having 1 to 8 carbon atoms.

When R ₁ of the ester is F, Cl or Br, preferred examples of the ester are ethylchloroformate or phenylchloroformate. R ₁ of the ester When, the preferred example of ester is di (t-butyl) dicarbonate.

According to the aforementioned method of the present invention, the obtained polyhydroxystyrene derivative has the structure shown in the following formula (2).

[Formula 2]

In the formula,

R ₂ is a hydrocarbon group selected from the group consisting of a hydrocarbon group having 1 to 8 carbon atoms, preferably alkyl, phenyl, benzyl, substituted alkyl, substituted phenyl, and substituted benzyl having 1 to 8 carbon atoms.

Substituted phenyl may comprise one or two substituents. Similarly, substituted benzyl may also include one or two substituents. Substituents may be alkyl, alkoxy or halogen such as methyl, ethyl, propyl, methoxy, ethoxy, propoxy, fluorine, chlorine or bromine.

According to the following examples of the invention, R ₂ may be ethyl, t-butyl or phenyl.

In formula (2), the ratio of m / m + n is between 0 and 1, preferably between 0.05 and 0.95, which indicates that the partial functionalization degree of polyhydroxystyrene is between 5% and 95%.

According to one aspect of the invention, the present invention will use a special solvent system that allows the reaction to be carried out in a homogeneous manner so that the results (eg degree of functionality) of each polyhydroxystyrene molecule are not significantly different from each other. In addition, the solvents used are very low in toxicity and the reactions are carried out at room temperature, with no heating and reflux or low temperature equipment required for this kind of reaction. Thus, the method of the present invention is simple, high in safety and commercial value.

The polyhydroxystyrene derivative obtained from the present invention has a low absorption value at a wavelength of 248 nm and excellent thermal stability, and thus is suitable for use as a resin component of a 248 nm photoresist. Thus, according to the present invention, a polyhydroxystyrene derivative synthesized from the method of the present invention, and, based on the weight of the polyhydroxystyrene derivative, comprises 1-10% by weight of a photoacid generator and 5-30% by weight of a dissolution inhibitor. A photoresist composition is provided.

Acid generators suitable for use in the present invention may be diaryl iodonium salts, triaryl sulfonium salts, sulfonylhydroxyimide or derivatives thereof. Another suitable acid generator may be that used in European Patent No. 0634696. The dissolution inhibitor may be any compound comprising an labile functional group of an acid having a molecular weight of 1000 or less.

Numerous variations and variations are apparent to those skilled in the art, and the following examples are provided to more fully illustrate the methods and advantages of the present invention without limiting the scope thereof.

Example 1-5

Preparation of Polyhydroxystyrene Solution in Alcohol

2.8 g of potassium hydroxide was added to a flask containing 300 ml of ethanol. After complete stirring, 6.0 g of polyhydroxystyrene was added and stirred for another 1 hour at room temperature to make the solution clear. In addition to potassium hydroxide and ethanol, other alkali / alcoholic systems may also be used to dissolve polyhydroxystyrene. Table 1 lists suitable alkali / alcohol systems capable of dissolving polyhydroxystyrene.

TABLE 1

Example menstruum Alkali reagents One ethanol Potassium hydroxide 2 ethanol Sodium methoxide 3 ethanol Triethylamine 4 Methanol Sodium methoxide 5 Isopropanol Triethylamine

Example 6-9

Preparation of Polyhydroxystyrene Derivatives

0.4-1.0 equivalents of di (t-butyl) dicarbonate, ethylchloroformate or phenylchloroformate were added to the polyhydroxystyrene solution in the alcohol solution system obtained from one of Examples 1-5. After stirring for 6 hours, the mixture was concentrated under reduced pressure to remove some of the solvent. The resulting mixture was treated by addition of 100-500 ml of water, then acidified with traces of acetic acid, then filtered and dried to afford the desired product 1-4. The reaction scale, the weight of the product obtained and the equivalence ratio of the ester reagents are shown in Table 2.

TABLE 2

Example Ester reagent product number Weight (g) Scale (mall) Equivalent 6 Di (t-butyl) dicarbonate One 23.0 0.2 0.45 7 Di (t-butyl) dicarbonate 2 37.8 0.2 0.8 8 Ethylchloroformate 3 8.0 0.05 1.0 9 Phenylchloroformate 4 8.0 0.05 1.0

Example 10

5.6 g of potassium hydroxide was added to a flask containing 800 ml of ethanol. After complete stirring, 12.0 g of polyhydroxystyrene was added and stirred at room temperature for about 1 hour until the solution became clear. 0.8 equivalent of di (t-butyl) dicarbonate was added to the solution and stirred for a further about 6 hours. Then, 100 ml of N, N-dimethylformamide was added to increase the solubility of the resulting mixture and 0.4 equivalents of di (t-butyl) dicarbonate was added to provide the appropriate amount of reactant. The mixture was stirred for 6 hours, then 100 ml of water was added, filtered and dried under vacuum to give product 5 (20.3 g).

The product (polyhydroxystyrene derivative) obtained from the above example has the following formula (2).

Formula 2

The R ₂ and m / m + n ratios of each product are shown in Table 3.

TABLE 3

product R ₂ m / m + n Device for analyzing m / m + n One t-butyl 38.9% TGA 2 t-butyl 69.3% TGA 3 ethyl 70.1% NMR 4 Phenyl 66.5% NMR 5 t-butyl 92.5% TGA

Spectroscopic data of product 1-5 are analyzed by ¹ H-NMR and listed below:

Products 1, 2 and 5:

(CDCl ₃ , 200 MHz): 1.55 (9H, s, 3Me), 6.50 (2H, s, b, Ar), 6.85 (2H, s, b, Ar).

Product 3:

(CDCl ₃ , 200 MHz): 1.38 (3H, s, b, Me), 4.31 (2H, s, b, CH ₂ ), 6.53 (2H, s, b, Ar), 6.88 (2H, s, b, Ar).

Product 4:

(CDCl ₃ , 200 MHz): 6.48 (2H, s, b, Ar), 6.96 (2H, s, b, Ar), 7.15-7.41 (5H, m, Ph).

As described above, the present invention uses a special solvent system that allows the production reaction of polyhydroxystyrene derivatives to be carried out in a uniform manner, so that the functionalities of the respective polyhydroxystyrene molecules are not significantly different from each other, so that the quality of the product is effectively The solvent used is very low in toxicity, the reaction is carried out at room temperature and there is no heating and reflux or low temperature equipment is required for this kind of reaction. Thus, the method of the present invention is simple, high in safety and commercial value.

Claims (16)

(a) polyhydroxystyrene is added to an alkaline alcohol solution, wherein the alkaline alcohol solution is obtained by mixing an alkali reagent and an alcohol to form a homogeneous polyhydroxystyrene solution, (b) reacting the polyhydroxystyrene solution with an ester of the formula (1) to obtain a polyhydroxystyrene derivative, the method of producing a polyhydroxystyrene derivative. Formula 1 Where R ₁ is F, Cl, Br and Wherein R ₃ is a hydrocarbon group having 1 to 8 carbon atoms, R ₂ is a hydrocarbon group having 1 to 8 carbon atoms. The production method according to claim 1, wherein the alkali reagent is selected from the group consisting of an alkali metal compound and a base compound comprising a nitrogen atom. The production method according to claim 2, wherein the alkali metal compound is selected from the group consisting of hydroxides and alkoxides of alkali metals. 4. A process according to claim 3 wherein said alkali metal compound is selected from the group consisting of sodium hydroxide, sodium methoxide, sodium ethoxide and sodium t-butoxide. 4. A process according to claim 3, wherein said alkali metal compound is selected from the group consisting of potassium hydroxide, potassium methoxide, potassium ethoxide and potassium t-butoxide. The method of claim 2, wherein the nitrogen atom-containing base compound , , , , , , And Wherein R ₄ , R ₅ , R ₆ are selected from the group consisting of H and a hydrocarbon group having 1 to 4 carbon atoms, and X is O or N. The production method according to claim 6, wherein the base compound including a nitrogen atom is trimethylamine or triethylamine. The process according to claim 1, wherein the alcohol is an alcohol having 1 to 6 carbon atoms. 9. A process according to claim 8 wherein said alcohol is selected from the group consisting of methanol, ethanol and isopropanol. The process according to claim 1, wherein R ₂ is selected from the group consisting of alkyl, phenyl, benzyl, substituted alkyl, substituted phenyl and substituted benzyl having 1 to 8 carbon atoms. The process according to claim 1, wherein R ₃ is selected from the group consisting of alkyl, phenyl, benzyl, substituted alkyl, substituted phenyl and substituted benzyl having 1 to 8 carbon atoms. The process according to claim 10, wherein R ₁ of said ester is selected from the group consisting of F, Cl and Br. 13. A process according to claim 12, wherein said ester is ethylchloroformate or phenylchloroformate. The compound of claim 10, wherein R ₁ of the ester is Phosphorus manufacturing method. 15. The process according to claim 14, wherein said ester is di (t-butyl) dicarbonate. The photoresist composition of claim 1 comprising 1-10 wt% photoacid generator and 5-30 wt% dissolution inhibitor, based on the weight of the polyhydroxystyrene derivative, polyhydroxystyrene derivative.