Unimatec Co., Ltd

Hirosaki University

Katsuyuki Sato

Seiichiro Murata

Yoshiyama Kaneumi

Hideo Sawada

Masayosi Horiuti

Sumiko Mouri

Ji-Shan Jin

Satoshi Kurihara

Takeshi Fukushima

Satoru Saito

Takehiro Sonoi

Hideki Abe

Akihiko Ikeda

Haruyoshi Tatsu

Keisuke Kokin

Mitsuru Maeda

Daisuke Murai

Sunao Ikeda

Kimihiko Urata

A fluorine-containing boric acid PVB composite comprising a condensate of a fluorine-containing alcohol, boric acid and polyvinyl butyral, wherein the fluorine-containing alcohol is represented by the general formula:Rf(A-OH)wherein k is 1 or 2; when k is 1, Rf is a perfluoroalkyl group having 6 or less carbon atoms, a polyfluoroalkyl group in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by hydrogen atom or atoms, a polyfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, or a linear or branched, perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms, a perfluoroalkylene group having 6 or less carbon atoms and ether bonds; when k is 2, Rf is a linear or branched, perfluoroalkylene group or polyfluoroalkylene group, containing a perfluoroalkylene group having 6 or less carbon atoms and ether bonds; and A is an alkylene group having 1 to 6 carbon atoms.

Fluorine-containing boric acid PVB composite

Provided is a fluorine-containing diblock copolymer having good water and oil repellency by using, as a raw material, a fluorine-containing (meth)acrylic ester having low bioaccumulation potential. The fluorine-containing diblock copolymer is produced by: process (A) a process for producing a fluorine-containing diblock copolymer by polymerizing a fluorine-containing (meth)acrylic ester represented by the following formula (1) in the presence of a trithiocarbonic ester compound and a radical polymerization initiator and then polymerizing a non-fluorine vinyl-based monomer, or process (B) a process for producing a fluorine-containing diblock copolymer by polymerizing a non-fluorine vinyl-based monomer in the presence of a trithiocarbonic ester compound and a radical polymerization initiator and then polymerizing a fluorine-containing (meth)acrylic ester represented by the following formula (1). 

Fluorine-containing diblock copolymer

A composite material of resin&#x2014;fluorine-containing boric acid composite particles comprising a resin, and a condensate of boric acid and a fluorine-containing alcohol represented by the general formula R-A-OH (wherein Ris a perfluoroalkyl group having 6 or less carbon atoms, or a polyfluoroalkyl group, in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by a hydrogen atom or hydrogen atoms, and which contains a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms; and A is an alkylene group having 1 to 6 carbon atoms, or comprising a resin, and a condensate of boric acid, the said fluorine-containing alcohol and an alkoxysilane at a molar ratio of 1.0 or less based on the fluorine-containing alcohol. These composite materials of resin&#x2014;fluorine-containing boric acid composite particles has good adhesion to inorganic substrates, and the like.

Composite material of resin&#x2014;fluorine-containing boric acid composite particles

Fluorine-containing boric acid composite capsule particles comprising a condensate of a fluorine-containing alcohol, a guest compound, and boric acid particles, wherein the fluorine-containing alcohol is represented by the general formula:R-A-OHwherein Ris:

Fluorine-containing boric acid composite capsule particles

Disclosed is an emulsion formed using, as an emulsifier, 0.01 to 30 parts by weight of a perfluoroalkylethyl phosphonic acid salt represented by the general formula: CFCHCHP(O)(OM)(OM) [III] (M: a hydrogen atom, ammonium salt, or organic amine salt, M: an ammonium salt or organic amine salt, n: 1 to 6), based on 100 parts by weight of a perfluoropolyether oil represented by the general formula: RfO(CFO)(CFO), (CFO), Rf' [I] (Rf and Rf&#x2032;: C-Cperfluoroalkyl groups, p+q+r: 2 to 200) or the general formula: F(CFCFCFO)CFCF[II](n: 2 to 100), or a perfluorocarbon compound. In spite of using, as an emulsifier, a compound having a perfluoroalkyl group containing 6 or less carbon atoms, which is said to have low bioaccumulation potential, the emulsion exhibits excellent emulsification stability, and therefore can be effectively used as a surface-treating agent, such as a mold-releasing agent.

Emulsion and mold-releasing agent using the same

Disclosed is a fluorine-containing oligomer comprising a copolymer of a fluoroalkyl alcohol (meth)acrylic acid derivative represented by the general formula:CF(CHCF)(CFCF)(CHCH)OCOCR&#x2550;CH&#x2003;&#x2003;[I]wherein R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4; b is an integer of 0 to 3; and c is an integer of 1 to 3; and a (meth)acrylic acid derivative represented by the general formula:(CH&#x2550;CRCO)R'&#x2003;&#x2003;[II]wherein R is a hydrogen atom or a methyl group, m is 1, 2, or 3; and when m is 1, R&#x2032; is OH group, NHgroup that is unsubstituted or mono- or di-substituted with an alkyl group having 1 to 6 carbon atoms, or a monovalent group derived from an alkylene glycol or polyalkylene glycol group containing an alkylene group having 2 or 3 carbon atoms; when m is 2 or 3, R&#x2032; is a divalent or trivalent organic group derived from a diol or triol. The copolymerization reaction is performed using a hydrocarbon-based peroxide or azo compound polymerization initiator. Also disclosed are nano-silica composite particles formed as a condensate of the fluorine-containing oligomer and an alkoxysilane with nano-silica particles.

Fluorine-containing oligomer, nano-silica composite particles using the same, and methods for producing both

Disclosed is a fluorine-containing oligomer comprising a copolymer of a fluoroalkyl alcohol (meth)acrylic acid derivative of the formula: CF(CH)OCOCR&#x2550;CH[I], wherein R is a hydrogen atom or a methyl group, n is an integer of 1 to 10, and d is an integer of 1 to 6; and a (meth)acrylic acid derivative of the formula: (CH&#x2550;CRCO)R' [II], wherein R is a hydrogen atom or a methyl group, m is 1, 2, or 3; and when m is 1, R&#x2032; is &#x2014;OH group, NHgroup that is unsubstituted or mono- or di-substituted with an alkyl group having 1 to 6 carbon atoms, or a monovalent group derived from an alkylene glycol or polyalkylene glycol group containing an alkylene group having 2 or 3 carbon atoms; when m is 2 or 3, R&#x2032; is a divalent or trivalent organic group derived from a diol or triol. The copolymerization reaction is performed using a hydrocarbon-based peroxide or azo compound polymerization initiator. Also disclosed are nano-silica composite particles formed as a condensate of the fluorine-containing oligomer and an alkoxysilane with nano-silica particles.

Disclosed is an emulsion formed using, as an emulsifier, 0.01 to 30 parts by weight of a perfluoroalkylethyl phosphonic acid salt represented by the general formula: CFCHCHP(O)(OM)(OM) [III] (M: a hydrogen atom, ammonium salt, or organic amine salt, M: an ammonium salt or organic amine salt, n: 1 to 6), based on 100 parts by weight of a perfluoropolyether oil represented by the general formula: RfO(CFO)(CFO)(CFO)Rf' [I] (Rf and Rf&#x2032;: C-Cperfluoroalkyl groups, p+q+r: 2 to 200) or the general formula: F(CFCFCFO)CFCF[II] (n: 2 to 100), or a perfluorocarbon compound. In spite of using, as an emulsifier, a compound having a perfluoroalkyl group containing 6 or less carbon atoms, which is said to have low bioaccumulation potential, the emulsion exhibits excellent emulsification stability, and therefore can be effectively used as a surface-treating agent, such as a mold-releasing agent.

Provided is a fluorine-containing macroinitiator, particularly a fluorine-containing macroinitiator that enables production of a fluorine-containing block copolymer containing a non-fluorine vinyl-based monomer having a long side chain. The fluorine-containing macroinitiator includes a polymer represented by the following formula (1) and having a number-average molecular weight of 3,000 to 100,000. In the following formula (1), R, Rand Rare each a specific group, and Q is a polymer segment composed of a structural unit represented by the following formula (2). In the following formula (2), Ris a hydrogen atom or a methyl group, Rf is a fluoroalkyl group having a specific structure, and k is an appropriate integer that is not 0. 

Fluorinated-containing macroinitiator and production process for the same

Fluorine-containing nano composite particles comprising a condensate of a fluorine-containing alcohol represented by the general formula:R-A-OH&#x2003;&#x2003;[I]wherein Ris a perfluoroalkyl group or a polyfluoroalkyl group in which some of the fluorine atoms of the perfluoroalkyl group are replaced by hydrogen atoms, and A is an alkylene group having 1 to 6 carbon atoms; and an alkoxysilane, or fluorine-containing nano composite particles comprising a condensate of a fluorine-containing alcohol represented by the general formula:R'-A-OH&#x2003;&#x2003;[Ia]or the general formula:HO-A-R&#x2033;-A-OH&#x2003;&#x2003;[Ib]wherein R&#x2032; is a linear or branched perfluoroalkyl group containing an O, S, or N atom, R&#x2033; is a linear or branched perfluoroalkylene group containing an O, S, or N atom, and A is an alkylene group having 1 to 6 carbon atoms; and an alkoxysilane.

Fluorine-containing nano composite particles and method for producing the same

A polyfluoroalkylphosphonic acid ester represented by the general formula: CF(CHCF)(CFCF)(CHCH)P(O)(OR)(R is an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3) is produced by a process of reacting a polyfluoroalkyl iodide represented by the general formula: CF(CHCF)(CFCF)(CHCH)I with a trialkyl phosphite represented by the general formula: P(OR)or by a process of reacting a polyfluoro-1-alkene represented by the general formula: CF(CHCF)(CFCF)CH&#x2550;CHwith a dialkyl phosphite represented by the general formula: (RO)P(O)H.

Polyfluoroalkylphosphonic acid ester and process for producing the same

Disclosed is a method for producing an aqueous emulsion containing a fluorine-containing copolymer comprising, as copolymerizable monomers, (A) at least one of a perfluoroalkylalkyl acrylate and a corresponding methacrylate represented by the general formula: CFCHOCOCR&#x2550;CH, wherein R is hydrogen or methyl group, n is 4, 5, or 6, and m is 1, 2, 3, or 4; (B) benzyl acrylate or benzyl methacrylate; (C) a fluorine-free polymerizable monomer other than benzyl acrylate and benzyl methacrylate; and (D) a crosslinkable group-containing polymerizable monomer; the copolymer being produced by previously subjecting 10 to 80 wt. % of the total weight of component (A) and 0 to 60 wt. % of the total weight of component (B) to a first polymerization reaction using an emulsion polymerization method; and then subjecting the remaining components to a second polymerization reaction using an emulsion polymerization method; wherein an emulsifier is used in the emulsion polymerization reaction in an amount of 21 to 150 parts by weight based on 100 parts by weight of the total weight of polymerizable monomers (A) and (B) used in the first polymerization reaction.

Method for producing an aqueous emulsion

A water- and oil-repellent includes, as an active ingredient, a fluorine-containing copolymer including as a copolymer unit (A) at least one of perfluoroalkylalkyl acrylates and corresponding methacrylates, (B) benzyl acrylate or benzyl methacrylate represented by the general formula: CFCHOCOCR&#x2550;CH(wherein R represents a hydrogen atom or a methyl group; n represents 4, 5, or 6; and m represents 1, 2, 3, or 4), (C) a fluorine-free polymerizable monomer other than benzyl acrylate and benzyl methacrylate, and (D) a cross-linkable group-containing polymerizable monomer.

Water-and oil-repellent

A water- and oil-repellent comprising an aqueous dispersion of a fluorine-containing copolymer including as a copolymerization unit (a) a perfluoroalkylalkyl (meth)acrylate represented by the general formula CFCHOCOCR&#x2550;CH(wherein R represents hydrogen atom or methyl group; n represents 4, 5, or 6; and m represents 1, 2, 3, or 4), (b) benzyl (meth)acrylate, (c) a fluorine-free polymerizable monomer other than benzyl (meth)acrylate, and (d) a cross-linkable group-containing polymerizable monomer; and a blocked isocyanate added to the aqueous dispersion in a weight ratio of 0.05 to 3.0 to the weight of the solid content of the aqueous dispersion.

Growing community of inventors

Ibaraki, Japan

Katsuyuki Sato