JPH02270834A - Halogenated polynuclear phenol compound, production thereof and positive type resist composition using same compound - Google Patents

Abstract

NEW MATERIAL:A halogenated polynuclear phenol compound expressed by the formula (X is Cl or Br). EXAMPLE:2-(4-Hydroxyphenyl)-2-(2,4-dihydroxy-5-chlorophenyl)-propane. USE:Useful as a raw material of radiation sensitive ingredient for positive type resist. The above-mentioned compound expressed by the formula exhibits excellent resolving power and pattern form (profile). PREPARATION:4-Chlororesorcin or 4-bromoresorcin is reacted with 2-(4- hydroxyphenyl)-propene, e.g. using aluminum chloride as a catalyst and dioxane as a solvent, respectively at a reaction temperature ranging from 50 deg.C to boiling point of dioxane, preferably 60-80 deg.C to provide the compound expressed by the formula. Furthermore, 4-chlororesorcin is used at an amount of >=1.2mol based on 1mol 2-(4-hydroxyphenyl)-propene.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a compound used as a raw material for a radiation-sensitive component for a positive resist, a method for producing the same, and a positive resist using an ester form of the compound. The present invention relates to a resist composition.

<Prior Art> Conventionally, a condensate of a phenol compound and a quinonediazide compound has been used as a radiation-sensitive component for positive resists. As this phenol compound, trihydroxybenzophenone, tetrahydroxybenzophenone, etc. are used.

<Problems to be Solved by the Invention> However, resists containing radiation-sensitive components synthesized from these benzophenone compounds have problems in resolution and pattern shape (profile).

An object of the present invention is to provide a phenolic compound with which resists with improved performance can be made. For this purpose, as a result of intensive studies, we developed a compound that is the product of the present invention.

<Means for Solving the Problems> The present invention provides a compound represented by the following formula (r), 2-(4
-hydroxyphenyl)-2-(2,4-dihydroxy-5-chlorophenyl)-propane and 2-(4-hydroxyphenyl')-2-(2°4-dihydroxy-5
-bromophenyl)-propane.

(However, in the formula, X represents CI or Br.) This compound combines 4-chlororesorcin or 4-bromoresorcin and 2
It can be synthesized by reacting -(4-hydroxyphenyl)-propene.

The solvent used in this reaction may include dioxane, acetic acid, nitrobenzene, monochlorobenzene, water, etc. depending on the combination with the catalyst, but dioxane is preferred. Depending on the combination with the solvent, the catalyst may include aluminum chloride, various complexes of boron trifluoride, sulfuric acid chloride, zinc chloride, sulfuric acid, etc., but aluminum chloride is preferred.

Suitably, the concentration of the solvent is 2 to 5 times that of the raw material in terms of weight ratio.

When reacting with a dioxane solvent and an aluminum chloride catalyst, the reaction temperature can be selected from 50°C to the boiling point of dioxane depending on the amount of the melting medium, but 60 to 80°C is preferable.

The reaction molar ratio is 1.2 or more for 4-chlororesorcin or 4-bromoresorcin and 0.2 for aluminum chloride to 1 mole of 2-(4-hydroxyphenyl)-propene.
05 to 2.0 is possible, but 2.5 to 4.0, respectively.
0.0.8 to 0.6 is preferred.

The compound of the present invention is subjected to a condensation reaction with a quinonediazide compound and used as a radiation-sensitive component for positive resists.

The radiation-sensitive component for positive resists can be synthesized using a known method, that is, 2-hydroxyphenyl-2-dihydroxyphenyl-propane having the structure of formula (1) and a quinonediazide compound (for example, naphthoquinone-(1, 2)
-Diazide- (2) -5-sulfonic acid chloride) is condensed using dioxane or the like as a solvent by dropping a basic catalyst such as triethylamine, and then charged to ion-exchanged water to precipitate crystals, filtered, After drying, the radiation-sensitive component can be obtained.

The quinonediazide compound used for the synthesis of the radiation-sensitive component is naphthoquinone-(1,2)-diazide-(2).
-5-sulfonic acid chloride, naphthoquinone-(1,2)
Examples include -diazide-(2)-4-sulfonic acid chloride and benzoquinone-(1,2)-diazide-(21-4-sulfonic acid chloride).

<Effects of the Invention> The compound obtained by the condensation reaction of the compound of the present invention and a quinonediazide compound is used as a radiation-sensitive component of a positive resist, and a positive resist containing this radiation-sensitive component has excellent resolution and pattern. Indicates the shape (profile).

<Examples> Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples.

Example 1 1.545' of aluminum chloride was added to 40 g of dioxane, and the temperature was raised to 60 to 65°C while stirring to form a homogeneous solution. To this, 10 parts of 4-chlororesorcin was added, and 8,092 parts of 2-(4-hydroxyphenyl)-propene was added to 1 part of dioxane.
A solution of 0.2 and 0.0% was added dropwise over 1 hour.
Stirred for 7 hours. During the reaction, the temperature was kept at 60±8°C.

After the reaction was completed, the mixture was cooled to room temperature, 220 g of chloroform was added, stirred, and insoluble materials were removed from the P solution, followed by extraction by adding 600 g of water to the P solution. The chloroform layer was washed with 6009 water and concentrated to precipitate crystals. The crystal obtained by filtration had a molecular weight of 1.849 after drying at 60°C, and °HNMR confirmed that it was a compound having the structure of the following formula (]0.
Confirmed by spectrum, mass spectrum, IR spectrum and melting point.

'HNMR spectrum (solvent: acetone d6.TMS)
Chemical shift value δ (ppm): 1.5B (s, 6H), 6
．． 45 (S, IH), 6.69 (d, 2H)
, 7.05 (d, 2H) , 7.20 (S, LH
), 7.66 (S, IH), 8.01 (8,
IH) 8.82 (s, IH) Mass spectrum m/e 278 (M) IR spectrum sea 8000-8600 (OH) Melting point 196
~198°C Example 2 1.17 F of aluminum chloride was added to 40y of dioxane, and the temperature was raised to 60 to 65°C with stirring to form a homogeneous solution. Add 107 of 4-bromoresorcin to this, and add 2,877 of 2-(4-hydroxyphenyl)-propene to 1 of dioxane.
A solution dissolved in 0.07 was added dropwise over 1 hour, and then a solution of 0.07 was added dropwise over 1 hour.
Stirred for 5 hours. During the reaction, the temperature was kept at 60±8°C.

After the reaction was completed, the mixture was cooled to room temperature, 22 (l) of chloroform was added, stirred, and the insoluble materials were separated in a furnace. 60 (l) of water was added to the fP solution for extraction. After washing the chloroform layer with 6,002 l of water, Upon concentration, crystals were precipitated. The crystals obtained by filtration had a molecular weight of 0.929 after drying at 60°C, indicating that this was a compound having the structure of the following formula (Ill).
Confirmed by MR spectrum, mass spectrum, IR spectrum and melting point.

"HNMR spectrum (solvent: acetone ds, TMS
) Chemical shift value δ (ppm): 1.6B (s, 6H), 6.
46 (s, tH), 6.69 (a, 2H), 7
．． 04 (d, 2H), 7.35 (S, 18), 7.
69 (s, LH), 8.00 (s, LH), 8
．． 37 (s, IH) Mass spectrum m/e 822 (M) IR spectrum = 1 Sea 3000-3600 cm (OH) Melting point 10
6 to 107°C Synthesis Example 1 In a three-tube flask with an internal volume of soomt, the compound obtained in Example 1 was immersed in 7432, naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid, The reaction temperature was controlled at 20 to 25°C, and 5.869 g of triethylamine was added dropwise over 30 minutes using a dropping funnel. Thereafter, stirring was continued for 4 hours while maintaining the reaction temperature at 20 to 25°C. After the reaction, the mixture was charged into ion-exchanged water, filtered, and dried to obtain radiation-sensitive component A.

Synthesis Example 2 Instead of the compound represented by formula (I[J, formula (II)
A radiation-sensitive component was obtained in the same manner as in Synthesis Example 1 except that the compound represented by was used. The obtained radiation-sensitive component is
shall be.

Synthesis Example 8 A radiation-sensitive component was obtained in the same manner as in Synthesis Example 1, except that 2.8.4-trihydroxybenzophenone was used instead of the compound represented by formula (If). The obtained radiation-sensitive component is designated as C.

Synthesis Example 4 Instead of the compound represented by formula (Il), 2.8.4°4-tetrahydroxybenzophenone was replaced with naphthoquinone-
A radiation-sensitive component was obtained in the same manner as in Synthesis Example 1, except that the molar ratio with (1,2)-diazide-(2)-5-sulfonic acid chloride was 1:8. The obtained radiation-sensitive component is designated as D.

Next, the performance of a resist having radiation-sensitive components A and B as its components and a resist having radiation-sensitive components C and D as its components was compared in terms of r value and resolution.

Example 8.4 and Comparative Example 1 Base 2 Radiation-sensitive components A and B obtained in Synthesis Examples 1.2 and 8.4
, C, and D together with a novolac resin were dissolved in 48 parts of ethyl cellosolve acetate with the composition shown in Table 1 to prepare a resist solution. The prepared resist solution was filtered through a 0.2 pm Teflon filter to prepare a resist solution. This was coated to a thickness of 1.8 P on a silicon wafer cleaned by a conventional method using a spin coater. Next, this silicon wafer was heated on a hot plate at 100℃ for 6
Bake for 0 seconds. Then this wafer was exposed to 486 nm.
Exposure was carried out using a reduction projection exposure machine (GCA DSW4800NA-0,42) having a (2-line) exposure wavelength and changing the exposure amount stepwise. Add this to Sumitomo Chemical developer 5O
A positive pattern was obtained by developing with PD for 1 minute.

Next, the normalized film thickness (-residual film thickness/
The initial film thickness) was plotted, and its slope θ was determined, and tan θ was taken as the r value.

The results are shown in Table 1 along with the resolution obtained at the same time.

Table-1 Mine novolac resin metacresol/paracresol-778 cresol/
A novolac resin with a heavy charge average molecular weight of 9800 (polystyrene equivalent) obtained by reaction under reflux using an oxalic acid catalyst at a molar ratio of formalin-1/0.8.

[Brief explanation of drawings]

Figure 1 shows 2-(4-hydroxyphenyl)- of Example 1.
2-(2,4-dihydroxy-5-chlorophenyl)-
This is a 'HNMR spectrum of propane. Figure 2 shows 2-(4-hydroxyphenyl)- of Example 1.
2-(2,4-dihydroxy-5-chlorophenyl)-
This is an IR spectrum of propane. Figure 8 shows 2-(4-hydroxyphenyl)- of Example 2.
2-(2,4-dihydroxy-5-bromophenyl)-
This is a 'HNMR spectrum of propane. Figure 4 shows 2-(4-hydroxyphenyl)- of Example 2.
2-(2,4-dihydroxy-5-bromophenyl)-
Al in the IR spectrum of propane. (Left below) (1B complete)

Claims (1)

[Claims] (1) A halogenated polynuclear phenol compound represented by formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, X represents Cl or Br. (2) The method for producing the compound according to claim 1, which comprises reacting 4-chlororesorcin or 4-bromoresorcin and 2-(4-hydroxyphenyl)-propene in the presence of an acid catalyst. (3) A positive resist composition comprising a quinonediazide sulfonic acid ester of the compound according to claim 1.