KR100237123B1 - Process for preparing polyhydroxystyrene derivatives - 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 method for producing. 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, more specifically, to a polyhydroxystyrene derivative using an alkaline alcohol solution as a solvent for dissolving polyhydroxystyrene in order to react polyhydroxystyrene with an ester in a homogeneous system. It relates to a manufacturing method.

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 main component of the photoresist is a resin, the resin is a key element in improving the above-described properties, particularly etch resistance, adhesion and film homogeneity.

In general, polyhydroxy styrene copolymer is often used as the resin component of the photoresist because of low absorption and excellent thermal stability at a wavelength of 248nm. Typically, there are two methods for preparing polyhydroxystyrene copolymers (or derivatives). One of them is the direct polymerization of two different monomers. For example, US Pat. No. 4,775,730 describes a method of directly polymerizing a styrene derivative with another alkene derivative and subsequently hydrolyzing the resulting copolymer to obtain the desired product. This reaction is shown in Scheme 1 below.

J. Polym. Sci .: Part A; Polym. Chem. Ed. 1986, 24, 2971 describe a method of polymerizing two different styrene monomers and then selectively decomposing the functional group. This reaction is shown in Scheme 2 below.

Another method of preparing a polyhydroxystyrene copolymer is a method comprising using polyhydroxystyrene as a starting material and reacting it with an ester reagent. For example, European Patent No. 0634696 dissolves polyhydroxystyrene in tetrahydrofuran (THF) and then adds potassium t-butoxide [KOC (CH ₃ ) ₃ ] and adds the mixture to di (t-butyl) dica. A method of reacting with carbonate to obtain polyhydroxystyrene derivatives is described. However, under the above conditions, potassium salt of polyhydroxystyrene is not dissolved in THF. Therefore, 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.

In summary, the conventional methods for preparing polyhydroxystyrene derivatives are complex or time-consuming, and the reactions are carried out in a heterogeneous system, resulting in significantly different functionalities of each polyhydroxystyrene molecule. Quality is not easily adjusted.

Accordingly, an object of the present invention is to provide a method for easily preparing a polyhydroxystyrene derivative by solving the above problems.

The present invention uses a special solvent system so that the reaction is carried out in a uniform manner, 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, thereby improving the quality of the product. To effectively control it. In addition, the solvents used are very low in toxicity and the reaction is also carried out at room temperature, so that no heating, reflux or low temperature equipment is required for this kind of reaction. Thus, the reaction of the present invention is simpler, saves time, and has high safety and commercial value.

Method for producing a polyhydroxy styrene derivative according to the present invention for achieving 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.

(여기에서, R₃은 탄소 원자 수 1 내지 8인 탄화수소기임)으로 이루어진 군으로부터 선택되고, R₂는 탄소 원자 수 1 내지 8인 탄화수소기이다.Wherein R ₁ is F, Cl, Br and

Wherein R ₃ is a hydrocarbon group having 1 to 8 carbon atoms, and R ₂ is a hydrocarbon group having 1 to 8 carbon atoms.

The starting material used to prepare the polyhydroxystyrene derivatives according to the invention is commercially available polyhydroxystyrene. This polyhydroxy styrene is added to the alkaline alcohol solution and then thoroughly stirred to form a uniform polyhydroxy styrene 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 period of time. Water is added to precipitate the product, followed by filtration and drying to give a polyhydroxystyrene derivative.

If the OH groups are functionalized in a certain proportion, the product can be precipitated using the above alkali / alcohol solution system for synthesizing polyhydroxystyrene derivatives. Therefore, in order to obtain a polyhydroxystyrene derivative having a higher functionalization ratio, the polyhydroxystyrene solution is reacted with an ester, followed by the addition of an organic solvent to dissolve the product, and the addition of an ester reagent to provide a suitable reactant. Unreacted OH groups of polyhydroxystyrene can be further functionalized. As a result, the degree of functionalization of the final product can be increased. Suitable organic solvents include all kinds of solvents capable of dissolving polyhydroxystyrene derivatives. N, N-dimethylformamide (DMF) is a representative example.

Suitable alkaline 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.

,

및

으로 이루어진 군으로부터 선택된다.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 have the structure shown by formula (1).

[Formula 1]

(여기서에, R₃은 탄소원자 수 1 내지 8인 탄화수소기이고, 바람직하게는 알킬, 페닐, 벤질, 치환 알킬, 치환 페닐 및 탄소 원자 수 1 내지 8인 치환 벤질로 이루어진 군으로부터 선택된 탄화수소기임)으로 이루어진 군으로부터 선택되고, R₂는 탄소 원자 수 1 내지 8인 탄화수소기, 바람직하게는 알킬, 페닐, 벤질, 치환 알킬, 치환 페닐, 및 탄소 원자 수 1 내지 8인 치환 벤질로 이루어진 군으로부터 선택된 탄화수소기이다.Wherein 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 and, R ₂ is a carbon atom number of 1 to 8 hydrocarbon group, preferably alkyl, phenyl, benzyl, substituted alkyl, substituted phenyl, and the carbon atom number of 1 to 8, selected from the group consisting of substituted benzyl It is a hydrocarbon group.

인 경우, 바람직한 에스테르의 예는 디(t-부틸)디카르보네이트이다.When R ₁ of the ester is F, Cl or Br, examples of preferred esters are ethylchloroformate or phenylchloroformate. R ₁ of the ester

In the case of, examples of preferred esters are di (t-butyl) dicarbonate.

The polyhydroxystyrene derivative obtained according to the method of the present invention described above has a structure shown in the following formula (2).

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

The substituted phenyl may include one or two substituents. Similarly, the substituted benzyl may also include one or two substituents. The substituents here may be alkyl, alkoxy or halogen, for example 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 the formula (2), the ratio of m / m + n is between 0 and 1, preferably between 0.05 and 0.95, which means that the partial functionalization degree of polyhydroxystyrene is between 5% and 95%.

According to one aspect of the present invention, the use of a special solvent system that allows the reaction to be carried out in a uniform manner will result in such that the functionalities of the respective polyhydroxystyrene molecules are not significantly different from one another. In addition, the solvents used are very low in toxicity and the reaction is also carried out at room temperature, so that no heating, reflux or low temperature equipment is required for this kind of reaction. Thus, the process of the present invention is simpler, safer and of high commercial value.

The polyhydroxystyrene derivatives obtained by the present invention are suitable for use as the resin component of the 248 nm photoresist because of low absorption and superior thermal stability at a wavelength of 248 nm. Thus, according to the present invention, polyhydroxystyrene derivatives synthesized by the method of the present invention, and 1-10% by weight of the photoacid generator and 5-30% by weight of the dissolution inhibitor based on the weight of the polyhydroxystyrene derivative 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 EP 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 modifications and variations will be 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 it was stirred thoroughly, 6.0 g of polyhydroxystyrene was added and stirred for an additional about 1 hour at room temperature until the solution became 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.

Example 6-9

[Production 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 any one of Examples 1-5. After stirring for 6 hours, the mixture was concentrated under reduced pressure to remove some solvent. 100-50 ml of water was added to the resulting mixture, which was then acidified with a small amount of acetic acid, which was then filtered and dried to afford the desired product 1-4. Table 2 lists the reaction scale, the weight of the product obtained and the equivalence ratio of the ester reagents.

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 equivalents of di (t-butyl) dicarbonate was added to this solution and stirred for about 6 hours. Subsequently, 100 ml of N, N-dimethylformamide was added to increase the solubility of the mixture thus obtained, and then 0.4 equivalent of di (t-butyl) dicarbonate was added to provide an appropriate amount of reactant. The mixture was stirred for 6 hours, then 100 ml of water was added, filtered and dried in vacuo to give the product 5 (20.3 g).

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

[Formula 2]

Table 3 lists the R ₂ and m / m + n ratios of each product.

The data listed below are spectral data for product 1-5 by ¹ H-NMR analysis:

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 which 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 as to improve the quality of the product. Effectively controllable, furthermore the toxicity of the solvent used is very low and the reaction is also carried out at room temperature so that no heating, reflux or low temperature equipment is required for this kind of reaction. As a result, the method of the present invention is simple, safe and of high commercial value.

Claims (16)

Polyhydroxystyrene is added to (a) an alkaline alcohol solution (the alkaline alcohol solution is obtained by mixing an alkali reagent and an alcohol) to form a homogeneous polyhydroxystyrene solution, and (b) a polyhydroxystyrene solution A method for producing a polyhydroxystyrene derivative, comprising reacting with an ester of Formula 1 to obtain a polyhydroxystyrene derivative that is a random polymer of Formula 2. [Formula 1]

[Formula 2]

Wherein 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, and m / (m + n) is 0.05 to 0.95 . 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.