Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Definitions

• the present invention relates to a sulfobetaine group-containing organosilicon compound having a sulfobetaine structure and a method for producing the same.
• a betaine compound is an amphoteric compound having a positively charged site and a negatively charged site at positions that are not adjacent to each other in the same molecule, and is an electrically neutral compound as a whole molecule.
• positively charged sites include quaternary amines, sulfonium, and phosphonium, and examples of negatively charged sites include carboxyl groups and sulfo groups.
• Patent Document 1 discloses a betaine-based silicon compound having a quaternary amine as a positive charge site and a carboxyl group as a negative charge site
• Patent Document 2 discloses a quaternary amine as a positive charge site and a negative
• a sulfobetaine-based silicon compound having a sulfo group as a charge site is disclosed.
• Organosilicon compounds having hydrolyzable functional groups are also used in coating compositions that are applied to the surfaces of substrates such as those made of glass or resin. Therefore, the organosilicon compound having a betaine structure can control the hydrophilicity of the coating composition, and is expected to impart high functionality to various substrate surfaces.
• the betaine-based or sulfobetaine-based silicon compounds disclosed in Patent Documents 1 and 2 can impart hydrophilicity, antistatic properties, antifouling properties, biocompatibility, etc. to the surface of substrates. was inadequate. Moreover, since these silicon compounds are deliquescent and hydrolyzable, it has been difficult to synthesize and isolate a silicon compound having a hydrophilic group that can be expected to have higher performance.
• the present inventors have made intensive studies on sulfobetaine-based organosilicon compounds that have improved bonding functions to substrates and anti-fogging functions. Both the group and the sulfobetaine structure that exerts the function of imparting hydrophilicity, antistatic properties, antifouling properties, biocompatibility, and especially antifogging properties to the substrate surface are bonded with a specific spacer. We succeeded in synthesizing sulfobetaine group-containing trialkoxysilane compounds.
• the sulfobetaine group-containing trialkoxysilane compound of the present invention is prepared by combining a trialkoxysilane having a tertiary amine and an electrophilic agent having a sulfonyl group precursor such as a halogenated alkylsulfonate and a cyclic sultone compound with acetone or acetonitrile. , ethanol, methanol, 2-propanol, tetrahydrofuran, and water.
• the sulfobetaine group-containing trialkoxysilane compound of the present invention has higher bonding properties to substrates and anti-fogging properties than conventional ones, and a sulfobetaine-based organosilicon compound can be obtained in a solid form.
• R 1 , R 2 and R 3 are independently C 1 -C 3 alkyl groups, or together with the ):
• Y is -NH-, -O- or -S-
• Z is
• R 4 and R 5 are independently C 1 -C 3 alkyl groups or formula (8):
• R 7 and R 8 are independently C 1 -C 3 alkyl groups, h and i are independently any integers from 2 to 4, j is from 1 to 3 is any integer, wherein a plurality of h, i and R 7 may each be different.
• R 6 is a C 1 -C 4 sulfonylalkyl group, However, the case where R 4 and R 5 are both C 1 -C 3 alkyl groups is excluded.
• (B) X, R 4 , R 5 and the quaternized nitrogen atom to which they are attached are taken together to form Formula (9):
• An imidazolinium group-containing group represented by R 6 is a C 1 -C 4 sulfonylalkyl group. ;or, (C) X is the formula (10):
• R 4 and R 5 are independently C 1 to It is a C 3 alkyl group or a (poly)sulfobetaine group represented by formula (8), and R 6 is a C 1 to C 4 sulfonylalkyl group. ⁇ to provide a sulfobetaine group-containing trialkoxysilane compound.
• (poly)sulfobetaine group includes both a sulfobetaine group and a polysulfobetaine group, and the term “polysulfobetaine group” refers to a group having a plurality of sulfobetaine moieties.
• the sulfobetaine group-containing trialkoxysilane compound represented by formula (1) has formula (11):
• R 9 , R 10 , R 11 , R 12 and R 13 are independently C 1 -C 3 alkyl groups, p and q are independently any of 2-4 is an integer, and r is an integer of 1 to 3, wherein a plurality of p, q and R 12 may be different, respectively.
• R 14 and R 15 are independently C 1 -C 3 alkyl groups, u and v are independently any integers from 1 to 4, and w is from 2 to 4 is any integer of ), a phenoxy-based sulfobetaine group-containing trialkoxysilane compound (C).
• sulfobetaine group-containing trialkoxysilane compound represented by formula (1) examples include compounds 1 to 8 below.
• Compounds 1 to 5 each belong to the group of (poly)sulfobetaine group-containing trialkoxysilane compounds (A) represented by formula (11) or formula (12), and compounds 6 and 7 each have the formula ( 13) belongs to the group of imidazolinium-based sulfobetaine group-containing trialkoxysilane compounds (B) represented by formula (14), and compound 8 is a phenoxy-based sulfobetaine group-containing trialkoxysilane compound (C ) belongs to the group of
• the present invention provides a production method for obtaining the sulfobetaine group-containing trialkoxysilane compound represented by formula (1).
• the method for producing the sulfobetaine group-containing trialkoxysilane compound represented by formula (1) is not limited, but a typical production method will be described.
• the sulfobetaine group-containing trialkoxysilane compound represented by formula (1) is represented by formula (15):
• Reaction formula represented by can be synthesized by a sultonization reaction according to
• a trialkoxysilane having a tertiary amine may be a commercially available product, or may be synthesized by a known method using a commercially available product as a starting material.
• the electrophiles (E) having a sulfonyl group precursor used here include halogenated alkylsulfonates and cyclic sultone compounds. More preferred are 1,3-propanesultone and 1,4-butanesultone.
• Purification includes known methods such as column chromatography, salt exchange with ion exchange resin, reverse phase fractionation, distillation, and recrystallization. Purification by a crystallization method from an appropriate organic solvent is more preferred.
• the sulfobetaine group possessed by the sulfobetaine group-containing trialkoxysilane compound of the present invention imparts hydrophilicity, antistatic properties, antifouling properties, and biocompatibility to the surface of substrates such as those made of glass or resin. It has an action mechanism of reducing light scattering and imparting an anti-fogging action by forming a water film from dew condensation water droplets.
• the sulfobetaine group-containing trialkoxysilane compound of the present invention can be expected to have improved hydrophilicity and antifogging properties as compared to known compounds.
• the sulfobetaine group-containing trialkoxysilane compound of the present invention is a silicon-containing compound capable of increasing bonding points with the substrate surface and creating a hydrophilic surface for the purpose of making the substrate surface a high-performance anti-fogging surface. Can be used together.
• the silicon-containing compound mentioned here means a tetraalkoxysilane-based compound. silica sol and the like. Preferred are tetraalkoxysilanes having an alkoxy group having 1 to 3 carbon atoms and partially hydrolyzed oligomers of the tetraalkoxysilanes. More preferred are tetraethoxysilane and a methylsilicate oligomer which is a partially hydrolyzed oligomer of the tetraalkoxysilane.
• the present invention provides an antifogging coating composition containing the sulfobetaine group-containing trialkoxysilane compound of the present invention.
• the alkoxysilane groups of the sulfobetaine group-containing trialkoxysilane compound of the present invention are easily partially or wholly hydrolyzed by water molecules present in the coating composition or on the surface of the substrate, resulting in a hydrolyzate having a silanol group. is formed, followed by dehydration condensation with oxygen functional groups present on the substrate surface to form covalent bonds and bind to the substrate.
• the silatranyl group is one form of alkoxysilane group, and is partially or completely hydrolyzed in the coating composition under suitable temperature conditions in the presence of a suitable acid or base to obtain a hydrolyzate having a silanol group.
• the hydrolyzate having the silanol group exists as a single substance or as a condensate of two or more. Not only simple substances, but also these condensates form covalent bonds through dehydration condensation with oxygen functional groups present on the substrate surface, and bind to the substrate.
• the antifogging coating composition of the present invention further comprises a tetraalkoxysilane compound selected from the group consisting of a tetraalkoxysilane having an alkoxy group having 1 to 3 carbon atoms and a solvent-dispersed organosilica sol of the tetraalkoxysilane. can contain.
• a tetraalkoxysilane compound selected from the group consisting of a tetraalkoxysilane having an alkoxy group having 1 to 3 carbon atoms and a solvent-dispersed organosilica sol of the tetraalkoxysilane. can contain.
• the tetraalkoxysilanes are readily partially or totally hydrolyzed by water molecules present in the coating composition or on the surface of the substrate to form a hydrolyzate having silanol groups.
• two or more, for example, 2 to 6 hydrolyzates are condensed to form a hydrolyzed oligomer having a silanol group, followed by dehydration condensation with oxygen functional groups present on the substrate surface to form a covalent bond. Form and bond to the substrate.
• the hydrolyzate or condensate of the hydrolyzate of the sulfobetaine group-containing trialkoxysilane compound and the hydrolyzate or hydrolyzate of the tetraalkoxysilane form a condensate.
• the condensate of also forms a covalent bond through dehydration condensation with the oxygen functional groups present on the substrate surface and bonds to the substrate.
• the solvent used when the sulfobetaine group-containing trialkoxysilane compound of the present invention is reacted with the substrate surface to form a covalent bond is a solvent that sufficiently dissolves the sulfobetaine group-containing trialkoxysilane compound of the present invention.
• examples include acetone, acetonitrile, ethanol, methanol, 2-propanol, tetrahydrofuran, water, etc. and mixtures thereof.
• Preferred are ethanol/water mixtures, methanol/water mixtures, and 2-propanol/water mixtures. The ratio of these mixed liquids can be set arbitrarily.
• the hydrophilic, antistatic, antifouling, biocompatible or anti-biological properties can be obtained on the surface of a substrate made of glass or resin.
• a coating composition is prepared that is capable of imparting haze.
• the concentration of the sulfobetaine group-containing trialkoxysilane compound of the present invention in the coating composition can be arbitrarily set at a concentration of 0.1 to 1000 mmol/L, preferably 1 to 100 mmol/L. , more preferably 5 mmol/L.
• An acid or base catalyst can be added to the coating composition to facilitate hydrolysis of the alkoxysilane.
• Examples of acid catalysts include organic carboxylic acids, organic sulfonic acids, hydrogen chloride, sulfuric acid, nitric acid, phosphoric acid and the like, preferably acetic acid.
• Examples of basic catalysts include an aqueous ammonia solution, organic amines, sodium hydroxide, potassium hydroxide, and the like, preferably an aqueous ammonia solution.
• the alkoxysilane groups or silatranyl groups of the sulfobetaine group-containing trialkoxysilane compound of the present invention are partially or completely hydrolyzed by water molecules present on the coating composition or substrate to form silanol groups.
• Formation of covalent bonds by dehydration condensation between generated silanol groups and oxygen functional groups present on the surface of the substrate includes methods such as immersion, spin coating, and vapor deposition. °C for 1 hour to 1 day.
• the reaction can be further carried out at a temperature of room temperature to 130° C. for 1 minute to 1 day.
• Substrates on which silanol groups are present on the surface are suitable as substrates to be subjected to antifogging treatment using the antifogging coating composition of the present invention.
• Examples include soda lime glass, lead glass, and borosilicate glass.
• a substrate made of glass such as Further, it may be a material other than glass or a substrate that has been chemically or electrochemically treated by a known method for improving reactivity with silanol groups.
• Examples of such materials include synthetic resins such as polyethylene, polypropylene, polycarbonate, polyurethane, polystyrene, ABS, polyvinyl chloride, phenol resin, epoxy resin, and polyacetal.
• the present invention provides an antifogging coating film having a first film containing the antifogging coating composition of the present invention.
• the present invention provides an antifogging coating film having, in addition to the first film, a second film containing a tetraalkoxysilane having an alkoxy group having 1 to 3 carbon atoms or a partially hydrolyzed oligomer of the tetraalkoxysilane. I will provide a.
• the antifogging coating film including the first film and the second film
• the first film and the A second membrane is attached.
• the present invention in a fifth aspect, comprises a substrate and an anti-fogging coating film formed on the surface of the substrate, wherein the anti-fogging coating film comprises the anti-fogging coating composition of the present invention.
• An anti-fog treated substrate is provided having a first coating.
• the alkoxysilane group or silatranyl group of the sulfobetaine group-containing trialkoxysilane compound contained in the first film is partially or entirely hydrolyzed, or the partially or entirely hydrolyzed product.
• the first membrane is directly attached to the substrate surface by condensation of the condensate with the hydrolyzed oligomer and the silanol groups on the substrate surface.
• the antifogging treated base material of the present invention further comprises a second film containing a tetraalkoxysilane having an alkoxy group having 1 to 3 carbon atoms or a partially hydrolyzed oligomer of the tetraalkoxysilane.
• the first film and the second film are bonded by condensation with the partially hydrolyzed oligomer of the tetraalkoxysilane contained in the second film, and the tetraalkoxysilane contained in the second film
• the second film is directly attached to the substrate surface by condensation of partially hydrolyzed oligomers of alkoxysilanes and silanol groups on the substrate surface.
• the present invention provides, in a sixth aspect, a method for producing an anti-fogging treated substrate comprising a substrate and an anti-fogging coating film formed on the surface of the substrate, wherein to form a first film.
• one of the alkoxysilane group and the silatranyl group of the sulfobetaine group-containing trialkoxysilane compound contained in the first film partial or total hydrolyzate, or condensate of said partial or total hydrolyzate; partially hydrolyzed oligomer of said tetraalkoxysilane; or one of alkoxysilane group or silatranyl group of said sulfobetaine group-containing trialkoxysilane compound
• the condensation of the partial or total hydrolyzate with the partially hydrolyzed oligomer of the tetraalkoxysilane and the condensation of the silanol groups on the substrate surface directly bonds the first membrane to the substrate surface.
• an alkoxy group having 1 to 3 carbon atoms is added to the surface of the substrate before the step of forming the first film.
• forming a second film by depositing a composition containing a tetraalkoxysilane or a partially hydrolyzed oligomer of the tetraalkoxysilane, wherein the step of forming the second film includes: In the step of forming the first film by directly bonding the second film to the substrate surface by condensation of the contained partially hydrolyzed oligomer of tetraalkoxysilane and the silanol groups on the substrate surface, A partial or complete hydrolyzate of the alkoxysilane group or silatranyl group of the sulfobetaine group-containing trialkoxysilane compound contained in the first film, or a condensate of the partial or complete hydrolyzate; a partially hydrolyzed oligomer; or a conden
• the surface of the substrate can be made anti-fogging.
• the sulfobetaine group-containing trialkoxysilane compound of the present invention undergoes partial or complete hydrolysis by water molecules present in the antifogging coating composition or on the substrate surface to form a hydrolyzate having silanol groups.
• This silanol group is covalently bonded, for example, by dehydration condensation with oxygen functional groups present on the surface of a substrate made of glass or resin.
• the number of the sulfobetaine group-containing trialkoxysilane compounds bonded per unit area of the substrate surface is should be increased.
• the present inventors confirmed that the antifogging properties of the sulfobetaine group-containing trialkoxysilane compound of the present invention are improved by pre-coating the substrate surface with tetraalkoxysilane (data not shown). This is because the tetraalkoxysilane undergoes partial or complete hydrolysis easily by surrounding water molecules and the like, and then two or more, for example, 2 to 6 hydrolysates are condensed to form a silanol. It was speculated that the reason was the increased number of attachment points by producing hydrolyzed oligomers with groups.
• the surface of the substrate can It was demonstrated that anti-fogging and anti-fouling properties can be improved while maintaining the hydrophilicity of In particular, the antifogging property could be greatly improved.
• a sulfobetaine group-containing trialkoxysilane compound and a tetraalkoxysilane are used in combination, first, a thin film of tetraalkoxysilane is formed on the substrate surface, and then a sulfobetaine group-containing compound is formed thereon.
• a stepwise method of applying an anti-fog coating composition containing a trialkoxysilane compound; and applying an anti-fog coating composition containing a tetraalkoxysilane together with a trialkoxysilane compound containing a sulfobetaine group are included.
• the sulfobetaine group-containing trialkoxysilane compounds 1 to 8 of the present invention were synthesized according to the following synthetic scheme. In the synthesis examples, the following abbreviations may be used for each description. NMR: peak chemical shift ⁇ value (ppm) in 1 H-NMR at measurement frequency of 300 MHz in each deuterated solvent; MASS: ESI-MS [M+H] + .
• Amination reaction A mixture of (3-bromopropyl)trimethoxysilane (93.2 g), N,N,N'-trimethylethylenediamine (39.6 g) and tetrahydrofuran (120 ml) was stirred at room temperature for 2 days. The reaction mixture was stirred at 70° C. for 2 days. After cooling to room temperature, 5 mol/L sodium methoxide-methanol solution (73.7 g) was added and stirred for 30 minutes. The insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure.
• Triethanolamine (2.95 g) was added to the reaction mixture, and the mixture was further stirred at 110°C for 1 day. The reaction mixture was allowed to cool to room temperature and then concentrated under reduced pressure. [3-(2,8,9-Trioxa-5-aza-1-silabicyclo[3.3.3]undecane-1-yl)propoxy]phenyl ⁇ -N,N-dimethylmethanamine (180 mg) was colorless. Obtained as an oil. MASS: 367.
• a glass slide (Slide glass S1225, manufactured by Matsunami Glass Industry Co., Ltd.) was immersed in 10% sodium lauryl sulfate aqueous solution, purified water, and acetone at room temperature, and then in 15% sodium hydroxide aqueous solution at 50°C, in that order, and ultrasonicated for 10 minutes each. The treatment activated the surface of the slide glass.
• the slide glass was immersed in antifogging coating composition 1 overnight at room temperature.
• Anti-fogging treated glass 2 was obtained by treating in the same manner as in Example 1 except that this slide glass was immersed in anti-fogging coating composition 2 at 60° C. for 4 hours.
• Antifogging coating composition 3 was obtained by preparing a solution of L and adding 2 vol% of acetic acid thereto.
• Anti-fogging treated glass 3 was obtained by treating in the same manner as in Example 1 except that this slide glass was immersed in anti-fogging coating composition 3 at 60° C. for 4 hours.
• Antifogging coating composition 5 was obtained by doing so.
• Anti-fogging treated glass 5 was obtained by treating in the same manner as in Example 1 except that this slide glass was immersed in anti-fogging coating composition 5 at 60° C. for 4 hours.
• An antifogging coating composition 6 was obtained by adding An anti-fogging treated glass 6 was obtained in the same manner as in Example 1 except that this slide glass was immersed in the anti-fogging coating composition 6 at 60° C. for 4 hours.
• Anti-fogging treated glass 7 was obtained by treating in the same manner as in Example 1 except that this slide glass was immersed in anti-fogging coating composition 7 at 60° C. for 4 hours.
• Antifogging treated glass 8 was obtained by treating in the same manner as in Example 1 except that this slide glass was immersed in antifogging coating composition 8 at 60° C. for 4 hours.
• Table 1 shows the results of water contact angle measurement, antifogging property test, and antifouling property test on the antifogging treated glasses 1 to 10 obtained in Examples 1 to 8 and Comparative Examples 1 to 2, respectively.
• the compound of the present invention is a sulfobetaine-based organosilicon compound with high hydrophilicity, but can be obtained in powder form and imparts antifogging and antifouling properties to substrates. became.
• compounds 1 and 3 were found to impart superior antifogging properties to substrates than conventionally known sulfobetaine organosilicon compounds.
• an antifogging treated base material superior to that obtained by using the compound of the present invention alone can be produced.
• a sulfobetaine-based organosilicon compound having higher bonding properties to substrates and higher antifogging properties than conventional ones can be obtained in a powder form, so that a coating composition having improved antifogging properties can be produced at a high level. It can be manufactured with productivity.

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