JP2003292526A - Method for producing solid resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a solid resin having good filterability even when the content of the solid resin in a solid resin-containing slurry is high. <P>SOLUTION: The method for producing the solid resin comprises reacting one or more kinds of monomer compounds in the presence of a reaction solvent to provide a resin-containing solution, adding the resin-containing solution to a solvent different from the reaction solvent to provide the slurry comprising the solid resin, and a mixed solvent of the reaction solvent and the solvent different from the reaction solvent, and substituting the mixed solvent in the obtained slurry with a cleaning solvent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a solid resin, and more specifically, to reacting one or more monomer compounds in the presence of a reaction solvent to obtain a resin-containing solution, The present invention relates to a method for producing a solid resin, which comprises adding the resin-containing solution to a solvent different from the reaction solvent to obtain a slurry comprising the solid resin, the reaction solvent, and a mixed solvent of the reaction solvent and a solvent different from the reaction solvent.

[0002]

2. Description of the Related Art Conventionally, a solid resin is obtained by reacting one or more monomer compounds in the presence of a reaction solvent to obtain a resin-containing solution, and then the resin-containing solution is used as the above-mentioned reaction solvent. It was produced by filtering solid resin-containing slurries obtained by adding it to different solvents (for example, JP-A-9-
90637).

[0003]

DISCLOSURE OF THE INVENTION The present inventors have found that when the slurry obtained by adding a resin-containing solution to a solvent different from the above-mentioned reaction solvent has a large amount of solid resin, the filterability deteriorates and the desired amount We have found that the filtration time required to obtain a solid resin is significantly delayed. The present invention provides a method for producing a solid resin having good filterability even when the solid resin-containing slurry has a large amount of solid resin.

As a result of further investigation based on the above findings, the present inventor reacted one or more monomer compounds in the presence of a reaction solvent to obtain a resin-containing solution, and then the resin-containing solution. It was found that a solid resin having a good filterability can be produced by adding a solution containing a solution to a solvent different from the reaction solvent to obtain a solid resin-containing slurry, and replacing the mixed solvent in the slurry with a washing solvent and then filtering. The present invention has been completed.

[0005]

That is, according to the present invention, a resin-containing solution is obtained by reacting one or more kinds of monomer compounds in the presence of a reaction solvent, and then the resin-containing solution is treated as described above. Addition to a solvent different from the reaction solvent to obtain a slurry comprising a solid resin and a reaction solvent and a mixed solvent of a solvent different from the reaction solvent, and further, the mixed solvent in the obtained slurry as a washing solvent. The present invention provides a method for producing a solid resin, which is characterized by substitution. Hereinafter, the present invention will be described in detail.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The solid resin produced in the present invention includes, for example, a resin which is a constituent component of a photoresist composition used when etching an electronic circuit pattern on a silicon wafer. Examples of the solid resin include R.I. D. Allen, W.C. Con
ley and J. D. Gelorme, Proc.
SPIE, 1672, 513 (1992), S.M. Takechi,
M. Takahashi, A .; Kotachi, K .; N
ozaki, E .; Yano and I. Hanyu,
J. Photopolym. Sci. Technol.,
7, 1, 31 (1994), K.S. Nakano, K .; Maed
a, Sci. Resins described in documents such as Technol., 10, 4, 561 (1995), resins described in JP 2000-137327 A, resins described in JP 9-90637 A and JP 11 The resins and the like described in JP-A-305444 can be mentioned.

The method for producing the solid resin of the present invention includes one kind or two kinds.
A step of obtaining a resin-containing solution by reacting one or more kinds of monomer compounds in the presence of a reaction solvent [hereinafter referred to as the first step], the resin-containing solution obtained in the first step in a solvent different from the above reaction solvent To obtain a slurry comprising a solid resin, a reaction solvent and a mixed solvent of a solvent different from the reaction solvent [hereinafter referred to as the second step], the mixed solvent in the slurry obtained in the second step It includes a step of replacing with a washing solvent [hereinafter referred to as a third step].

Examples of the one or more kinds of monomer compounds in the first step include raw material monomers used when producing the resins described in the above-mentioned documents and publications. Examples of the raw material monomer include unsaturated carboxylic acid esters and / or unsaturated carboxylic acid anhydrides, but the raw material monomers are two or more kinds, and at least one kind of the monomer is an unsaturated carboxylic acid ester. Is preferred. The unsaturated carboxylic acid ester is preferably an acrylic acid ester or a methacrylic acid ester, and the unsaturated carboxylic acid anhydride is preferably maleic anhydride or phthalic anhydride. The reaction in the first step may be carried out in the presence of a polymerization initiator. Examples of the polymerization initiator include 2,2′-azobis (isobutyronitrile) and the like.

The reaction solvent used in the first step is
For example, a ketone solvent such as methyl isobutyl ketone,
Examples include ether solvents such as tetrahydrofuran and dioxane. As the reaction solvent, a ketone solvent is particularly preferable. The amount of the reaction solvent used is not particularly limited,
The range of 200 to 1000 parts by weight is preferable per 100 parts by weight of the solid resin described in the above-mentioned documents and publications. When the solid resin obtained by the present invention is a constituent component of the photoresist composition, it is preferable that the solvent component and the reaction solvent constituting the above composition are different from each other.

The second step is a step of adding the solid resin-containing solution obtained in the first step to a solvent different from the reaction solvent and precipitating the solid resin to obtain a slurry containing the resin. Examples of the solvent different from the reaction solvent include alcohol solvents such as methanol and isopropanol, and a mixture of water and an alcohol solvent. The amount of the solvent different from the reaction solvent is preferably 350 parts by weight or more, based on 100 parts by weight of the resin-containing solution, and 350 to
A range of 1000 parts by weight is particularly preferred.

The third step is a step of replacing the mixed solvent in the slurry obtained in the second step with a washing solvent.
In the third step of replacing the mixed solvent with the cleaning solvent, it is not necessary to replace the entire amount of the mixed solvent with the cleaning solvent.
The replacement of the mixed solvent with the washing solvent is performed by, for example, a method of simultaneously removing the mixed solvent from the slurry obtained in the second step and adding the washing solvent to the remaining solid resin in parallel. . With respect to 100 parts by weight of the washing solvent to be added, it is preferable to remove 20 parts by weight or more of the mixed solvent from the slurry, and particularly, to remove 70 parts by weight or more of the mixed solvent from the slurry, per 100 parts by weight of the washing solvent. Is preferred. The method of removing the mixed solvent from the slurry obtained in the second step is not particularly limited, but a discharge port for the mixed solvent is provided on the side wall of the stirring tank, and the mixed solvent overflows from the discharge port. Alternatively, the discharge tube may be removed by weakening the pressure from the insertion port of the lid of the stirring tank into the stirring tank, and the supernatant liquid may be withdrawn. The time required to remove the mixed solvent from the slurry obtained in the second step is preferably shorter.

When the sedimentation rate of the solid resin is relatively high, it is preferable to replace the solvent with stirring, and when the sedimentation rate of the solid resin is relatively low, it is preferable to perform the natural sedimentation. The solvent different from the reaction solvent and the washing solvent are preferably the same as each other, and the amount of the washing solvent at the time of replacing the solvent is more than the mixed solvent amount of the solvent different from the reaction solvent and the reaction solvent remaining in the slurry. It is particularly preferable that the amount is large. The temperature at the time of solvent substitution is preferably 40 ° C or lower, more preferably 20 ° C or lower.

The solid resin obtained by the production method of the present invention can be easily isolated by a means such as filtration of the slurry obtained after the above solvent substitution. Examples of the filter used for isolating the solid resin include a vacuum filter and a pressure filter. The solid resin is dried if necessary after filtration.

[0014]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, "part" represents part by weight.

Example 1 (First Step) 2-Ethyl-2-adamantyl methacrylate 490 parts, 3-hydroxy-1-adamantyl acrylate 890 parts, 2-norbornene 565 parts, maleic anhydride 294 parts and methyl isobutyl ketone. 2390
The parts were mixed and dissolved. This is designated as [monomer solution]. 50 parts of azobisisobutyronitrile were dissolved in 853 parts of methyl isobutyl ketone. This is referred to as [polymerization initiator solution]. The [polymerization initiator solution] was degassed with nitrogen gas and heated to 80 ° C. At this temperature, [monomer solution]
Was added. After the addition was completed, the mixture was stirred at 80 ° C for 15 hours.
Then, the mixture was cooled to 60 ° C., 5200 parts of methyl isobutyl ketone was added at this temperature, and the mixture was washed 3 times with 2200 parts of ion-exchanged water. Then concentrate under reduced pressure to remove the solvent 71
00 parts were distilled off. This concentrated solution is referred to as <resin-containing solution 1>
And

(Second Step) The resin-containing solution 1 obtained in the first step was added at 20 ° C. to 18320 parts of methanol. The resulting slurry was stirred at 20 ° C. for 1 hour. After stirring, the mixture was left for 5 minutes.

(Third Step) After inserting the extraction tube into the liquid portion of the slurry obtained in the second step, the inside of the extraction tube was slightly depressurized to withdraw 17,000 parts of the supernatant layer. After withdrawing, 17,000 parts of methanol was immediately added to the residual liquid while stirring.

10 L of the slurry obtained after the addition of methanol was added to 0.25 to 0.25 using a 0.2 mφ filter.
It was filtered with a pressure difference of 0.3 Kg / cm ² . The time required for filtration was 1 minute. The material on the filter was washed twice with methanol. Next, the rest of the slurry obtained after the addition of methanol was filtered under the same conditions as above, washed and dried to obtain 970 parts of solid resin A.

Reference Example 1 The amount of impurities in Resin A obtained in Example 1 was 0.2% when analyzed by liquid chromatography. A photoresist composition was prepared using Resin A by a conventional method, applied on a silicon wafer, and then etched by a conventional method to form an electronic circuit pattern. The pattern had good resolution.

Comparative Example 1 Resin-containing solution 1 obtained by the same operation as in the first step of Example 1 was added to 18320 parts of methanol at 20 ° C. The obtained slurry was stirred at the same temperature for 1 hour. Next, 10 L of the slurry obtained by stirring was filtered with a 0.2 mφ filter at a pressure difference of 0.25 to 0.3 Kg / cm ² . The time required for filtration was 5 hours. The material on the filter was washed twice with methanol. The resin-containing solution 1 was added to 18320 parts of methanol at 20 ° C., and the resulting slurry was stirred for 1 hour at the same temperature. Then, the rest of the slurry was filtered, washed and dried under the same conditions as above. 970 parts of solid resin A'was obtained.

Reference Comparative Example 1 The amount of impurities in the resin A ′ obtained in Comparative Example 1 was analyzed by liquid chromatography and found to be 1.1%. Resin A '
Was used to prepare a photoresist composition by a conventional method, which was applied on a silicon wafer and then etched by a conventional method to form an electronic circuit pattern. The resolution of the above pattern was not sufficient.

Example 2 (First Step) The same procedure as in the first step of Example 1 was repeated to obtain a resin-containing solution 1. (Second step) The resin-containing solution 1 obtained in the first step was added to 18320 parts of methanol at 20 ° C. The resulting slurry
The mixture was stirred for 1 hour while maintaining it at 20 ° C. After stirring, 6
Let stand for a minute. (Third step) Next, a withdrawal tube was inserted into the liquid portion, the inside of the withdrawal tube was depressurized, and 8400 parts of the supernatant layer was withdrawn. After withdrawing, 17,000 parts of methanol was immediately added while stirring the residual liquid. 200 L of the obtained slurry
0.25 to 0.3 Kg using a 0.5 m ² filter
It was filtered with a pressure difference of / cm ² . The time required for filtration was 6 minutes. The material on the filter was washed twice with methanol. Thereafter, in the same manner as in Example 1, 970 parts of a solid resin was obtained.

[0023]

According to the present invention, a solid resin having good filterability can be easily produced. Further, the solid resin having good filterability has a small amount of impurities. Therefore, when a photoresist composition is prepared using the solid resin obtained by the present invention, an electronic circuit pattern having excellent resolution can be obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takuji Fujisawa             3-1,98-1 Kasugade, Konohana-ku, Osaka             Tomo Chemical Co., Ltd.

Claims (7)

[Claims] 1. A resin-containing solution is obtained by reacting one or more monomer compounds in the presence of a reaction solvent, and then the resin-containing solution is added to a solvent different from the above reaction solvent. To obtain a slurry comprising a solid resin and a reaction solvent and a mixed solvent of a solvent different from the reaction solvent, and further replacing the mixed solvent in the obtained slurry with a washing solvent. Manufacturing method. 2. The method according to claim 1, wherein the monomer compound is two or more kinds, and at least one kind of the monomer compound is an unsaturated carboxylic acid ester. 3. The method according to claim 2, wherein the unsaturated carboxylic acid ester is an acrylic acid ester or a methacrylic acid ester. 4. The method according to claim 3, wherein the acrylic acid ester is an ester of acrylic acid and an alicyclic alcohol, and the methacrylic acid ester is an ester of methacrylic acid and an alicyclic alcohol. 5. The method according to claim 1, wherein the reaction solvent is a ketone solvent or an ether solvent. 6. The method according to claim 1, wherein the solvent different from the reaction solvent is an alcohol solvent or a mixture of water and an alcohol solvent. 7. The method according to claim 1, wherein the washing solvent is an alcohol solvent or a mixture of water and an alcohol solvent.