Central Glass Company, Limited

The State University of New York

Ryo Nadano

Shinya Akiba

Yoshihiko Goto

Takeo Komata

Makoto Matsuura

Takashi Sakaya

Mineo Watanabe

Makoto Kobayashi

Satoru Miyazawa

Masatomi Kanai

Yutaka Katsuhara

Takayuki Nishimiya

Toshihiro Nakamichi

Yuzuru Kaneko

Asuka Sano

Yusuke Kuramoto

Tsubasa Itakura

Eri Nishizawa

Hitoshi Oomuro

Masaaki Takeda

Masafumi Hirotsu

Shigeru Suenaga

Asami Inazu

Robert L Brainard

The present invention is directed to a purification method for purifying a fluorine-containing polymerizable monomer of the formula (1), in which the fluorine-containing polymerizable monomer is purified by distillation in the coexistence of a phenolic compound A such as 6-tert-butyl-2,4-xylenol and a phenolic compound B such as 2,2'-methylene-bis(4-methyl-6-tert-butylphenol). By the combined use of the phenolic compound A and the phenolic compound B, it is possible to significantly suppress polymerization or oligomerization of the fluorine-containing polymerizable monomer even during industrial-production-scale distillation and efficiently purify the fluorine-containing polymerizable monomer by distillation.

Method for purifying polymerizable fluoromonomer by distillation

Provided is a fluorine-containing polymer which has no perfluoroalkyl group of 4 or more carbon atoms and which, when formed together with a photoacid generator into a film, shows water repellency after film formation, but becomes hydrophilic by the action of an acid generated under light irradiation, and thus serves as a pattern forming material capable of forming a film with high sensitivity and resolution. A fluorine-containing polymer according to the present invention has a repeating unit of the formula (1) where Ris a hydrogen atom, a fluorine atom or a C-Calkyl group; Rto Rare each independently a hydrogen atom or a C-Calkyl group; X is a single bond or a divalent group; Y is a C-Cfluoroalkyl or carboxylate (&#x2014;COOR) group; R is a C-Cfluoroalkyl group; and seven or less of hydrogen atoms contained in the substituent group may be substituted with fluorine.

Fluorine-containing monomer, fluorine-containing polymer, pattern forming composition using same, and pattern forming method of same

Disclosed is an industrial method for efficient production of an &#x3b1;,&#x3b1;-difluoroaldehyde compound, which includes reaction of an &#x3b1;,&#x3b1;-difluoroacetate with hydrogen gas (H) in the presence of a ruthenium catalyst and a base. By the adoption of specific reaction conditions (catalyst, base, pressure etc.), it is possible to produce the target &#x3b1;,&#x3b1;-difluoroaldehyde compound with a high conversion rate and high selectivity.

Method for producing &#x3b1;,&#x3b1;-difluoroacetaldehyde

A method for improving preservation stability of 2,2-difluoroacetaldehyde according to the present invention include at least: a first step of forming a '2,2-difluoroacetaldehyde-alcohol composite system' in which a 2,2-difluoroacetaldehyde hemiacetal coexists with an excess alcohol, wherein the total molar amount of the alcohol is 1.15 to 4.00 times the total molar amount of 2,2-difluoroacetaldehyde; and a second step of storing, in a storage container, the '2,2-difluoroacetaldehyde-alcohol composite system' formed in the first step. It is possible by this method to suppress the conversion of the 2,2-difluoroacetaldehyde hemiacetal to a dimer and maintain the original aldehyde activity of the target compound with less composition change over a long term.

Method for improving preservation stability of 2,2-difluoroacetaldehyde

As shown by the following reaction formula, disclosed is a fluorine-containing hydroxyaldehyde production method, including the step of obtaining a fluorine-containing hydroxyaldehyde represented by the general formula (1) by reacting a fluorine-containing ketone represented by the general formula (4) and an aldehyde represented by the general formula (5) in the presence of an organic base selected from a heterocyclic compound which contains a nitrogen atom in its ring or a tertiary amine. By this production method, it is possible to obtain the fluorine-containing hydroxyaldehyde in a high yield. Furthermore, it is possible to easily obtain in high yields a fluorine-containing propanediol, which is a derivative of this fluorine-containing hydroxyaldehyde, and a fluorine-containing alcohol monomer by using the same. 

Methods for producing fluorine-containing hydroxyaldehyde, fluorine-containing propanediol, and fluorine-containing alcohol monomer

A method of stabilizing a fluorine-containing acid amplifier. The method is provided to include the step of dissolving a fluorine-containing acid amplifier in an organic solvent thereby producing a solution of the fluorine-containing acid amplifier, the fluorine-containing acid amplifier being represented by general formula (1): 

Method of stabilizing fluorine-containing acid amplifier

According to the present invention, an &#x3b1;-substituted acrylic ester monomer for a fluorinated resist is produced by direct addition of an &#x3b1;-substituted acrylic acid to a fluorinated alkene in the presence of a specific acid catalyst having a sulfonyl group. By the use of such a specific acid catalyst, it is possible to achieve industrial-scale production of the &#x3b1;-substituted acrylic ester monomer for the fluorinated resist by carrying out the target addition reaction of the fluorinated alkene and the &#x3b1;-substituted acrylic acid efficiently during the occurrence of side reactions such as isomerization of the alkene, generation of a diol and excessive addition of the &#x3b1;-substituted acrylic acid.

Process for producing monomer for fluorinated resist

Disclosed is a process for producing &#x3b1;-substituted norbornanyl acrylates efficiently on an industrial scale while suppressing the formation of by-products derived from intramolecular cyclization, excessive addition to acrylic acid etc. The &#x3b1;-substituted norbornanyl acrylates are useful as norbornene resist monomers. In the disclosed process, an &#x3b1;-substituted acrylic acid is directly reacted with a substituted norbornene in the presence of at least one acid catalyst selected from methanesulfonic acid and camphorsulfonic acid. It is possible in this reaction to suppress the formation of the by-products derived from intramolecular cyclication, excessive addition of the acid to the reaction product etc.

Process for producing &#x3b1;-substituted norbornanyl acrylates

There is provided a process for producing a fluorine-containing alkylsulfonylaminoethyl &#x3b1;-substituted acrylate of the formula [3] by reaction of an aminoethyl &#x3b1;-substituted acrylate of the formula [1a] with a fluorine-containing alkylsulfonic fluoride of the formula [2], or by reaction of an aminoethyl a-substituted acrylate salt of the formula [1b] with a fluorine-containing alkylsulfonic fluoride of the formula [2] in the presence of a base, wherein a fluorine-containing compound is used as a reaction solvent: where Ris a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tertbutyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group or perfluoroethyl group; Ris a fluorine-containing alkyl group having a carbon number of 1 to 6; Xis a counter anion (n is a positive integer); and Y is a fluorine atom, chlorine atom or bromine atom.

Process for producing fluorine-containing alkylsulfonylaminoethyl &#x3b1;-substituted acrylate

The present invention provides a process for producing a fluorine-containing alkylsulfonylaminoethyl &#x3b1;-substituted acrylate represented by general formula [3]: which comprises reacting an aminoethyl &#x3b1;-substituted acrylate represented by general formula [1a] or a salt thereof: with a fluorine-containing alkylsulfonyl halide represented by general formula [2a] or a fluorine-containing alkylsulfonic anhydride represented by general formula [2b]: 

The invention relates to a process for producing 1,1,3,3-tetrachloro-1,3-difluoroacetone. This process includes fluorinating hexachloroacetone in a liquid phase by hydrogen fluoride in the presence of a catalyst containing a metal compound. This metal compound can be selected from tin halides, titanium halides, molybdenum halides, tungsten halides, niobium halides, tantalum halides, and iron halides. This process is suitable for producing 1,1,3,3-tetrachloro-1,3-difluoroacetone in an industrial scale.

Process for producing 1,1,3,3-tetrachloro-1,3-difluoroacetone

Process for producing 1,1,1-trifluoroacetone

A process of producing chlorofluoroacetones represented by a general formula

Process of producing chlorofluoroacetones

The invention relates to a method for producing 3,3-dichloro-1,1,1-trifluoroacetone. This method includes a step of fluorinating pentachloroacetone by hydrogen fluoride in the presence of a fluorination catalyst. This fluorination may be conducted in a liquid phase in the presence of an antimony compound as the fluorination catalyst. Alternatively, the fluorination may be conducted in a gas phase in the presence of a fluorination catalyst which may be a fluorinated alumina or at least one compound of at least one metal selected from Al, Cr, Mn, Ni, and Co. The method is suited to an industrial scale production of 3,3-dichloro-1,1,1-trifluoroacetone. The invention further relates to another method for producing 3,3-dichloro-1,1,1-trifluoroacetone. This method includes a step of purifying a crude 3,3-dichloro-1,1,1-trifluoroacetone by a distillation in the presence of water, thereby to produce 3,3-dichloro-1,1,1-trifluoroacetone which is substantially free of organic matters other than 3,3-dichloro-1,1,1-trifluoroacetone. This crude 3,3-dichloro-1,1,1-trifluoroacetone may be the reaction products of the fluorination of pentachloroacetone in a gas phase. Due to the provision of the another method, 3,3-dichloro-1,1,1-trifluoroacetone can be produced with high yield.

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Saitama, Japan

Ryo Nadano