Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/165—Ethers
  • D06M13/17—Polyoxyalkyleneglycol ethers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/53—Polyethers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

• the present invention relates to a water repellent composition. Specifically, the present invention relates to a water repellent composition that imparts high water repellency to fibers, and a fiber treatment agent containing the composition.
• fluorine-based compounds have been used as a method of imparting water repellency to natural fibers, synthetic fibers, leather, paper, etc.
• Textile products treated with a water repellent containing a fluorine compound as a main component have excellent water repellency and excellent durability.
• the range of application of fluorine-based compounds is limited because they are expensive and require treatment at high temperatures in order to exhibit high water repellency.
• fluorine compounds have a very stable structure and are difficult to decompose in the environment, and also have a tendency to accumulate, which poses environmental problems and their use is being regulated both domestically and internationally. Based on the above background, the development of water repellents that do not contain fluorine compounds is being considered.
• compositions containing silicone-based compounds such as silicone as a main component are being studied.
• Japanese Patent No. 2960304 discloses a composition containing an acrylic-silicone graft polymer compound as a main component
• Japanese Patent Application Publication No. 2018-104866 discloses a composition containing modified silica as a main component
• Japanese Patent No. 6573548 discloses a composition containing modified silica as a main component.
• compositions using silicone alkoxy oligomers and polyorganosilsesquioxanes have been studied.
• Silicon-based compounds can impart good flexibility and texture to textile products, and can also impart water repellency at the same time.
• the effect of imparting water repellency is enhanced by optimizing the composition of the silicon-based compound and each component, and the treated fibers exhibit excellent water repellency.
• none of the above-mentioned documents 1 to 3 mention flexibility or texture, leaving the problem of achieving both high water repellency and flexibility/texture.
• a water repellent composition is used for textile products, it is desirable that the water repellency is maintained even after washing.
• Patent Documents 1 to 3 do not discuss water repellency after washing.
• Patent No. 2960304 Japanese Patent Application Publication No. 2018-104866 Patent No. 6573548
• the present invention has an excellent water repellency imparting effect, can impart good flexibility and texture to treated fibers, and maintains good water repellency even after washing.
• An object of the present invention is to provide a water repellent composition that can be used in water repellent compositions, and a fiber treatment agent containing the water repellent composition.
• composition containing the following components (A) to (E) imparts high water repellency to fibers as well as good flexibility and texture. They discovered that good water repellency can be maintained even after washing, leading to the present invention.
• the present invention provides the following water repellent composition and fiber treatment agent.
• R 1 is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms
• R 2 is a hydrogen atom
• R 3 is independently R 1 and R 2
• a, b, c, d and e are 0 ⁇ a ⁇ 10, 0 ⁇ b ⁇ 100, 0 ⁇ c ⁇ 500, 0 ⁇ d
• It is a number that satisfies the following ranges: ⁇ 5, 0 ⁇ e ⁇ 5, 0 ⁇ a+b+c+d+e.However, if c 0, at least one of R3 is R2 .
• B (meth)acrylic polysiloxane represented by the formula and having a visco
• R 8 is a group independently selected from a phenylene group and an alkyleneoxycarbonyl group having 1 to 11 carbon atoms
• R 10 is an alkyl group having 1 to 30 carbon atoms, a hydroxyalkyl group, and hydrogen.
• a group selected from atoms, and X is -Si-(CH 3 ) 3-m (OR x ) m
• R x is a group selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group, and an aryl group having an alkyl substituent and an aralkyl group
• m is a group having 1 to 3 carbon atoms. is an integer, and when m is 2 or 3, R x may be different from each other.
• n represents an integer of 3 to 500.
• (C) Surfactant: 0.5 to 50 parts by mass, A water repellent composition containing (D) a condensation reaction catalyst: 0.1 to 100 parts by mass, and (E) water: 50 to 3,000 parts by mass. 2.
• (B) component is a (meth)acrylic polymer containing a structural unit selected from (B-1) and (B-3) among the above structural units (B-1) to (B-3), The water repellent composition according to 1 or 2. 4. 4.
• component (C) is one or more metal compounds selected from tin, zinc, bismuth, titanium, iron, zirconium, and aluminum. 5.
• component (C) is one or more metal compounds selected from tin, zinc, bismuth, titanium, iron, zirconium, and aluminum. 5.
• the water repellent composition according to any one of 1 to 4 wherein the content of the fluorine compound is less than 1 part by mass per 100 parts by mass of component (A).
• a fiber treatment agent comprising the water repellent composition according to any one of 1 to 5.
• the water repellent composition of the present invention can maintain good water repellency even after washing, and can impart high water repellency to fibers as well as good flexibility and texture.
• R 1 independently represents an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, cyclohexyl group.
• Alkyl groups such as , heptyl group, octyl group, nonyl group, decyl group, tetradecyl group, octadecyl group: Alkenyl groups such as vinyl group, allyl group, 5-hexenyl group, oleyl group: phenyl group, tolyl group, naphthyl group, etc. Examples include aryl groups. Among these, a methyl group, a long-chain (6 to 20 carbon atoms) alkyl group, and a phenyl group are preferred, and a methyl group is more preferred.
• R 2 is a hydrogen atom.
• 10% or more is preferably R 2 (hydrogen atom), and more preferably 15% or more is R 2 (hydrogen atom).
• 20% or more is R 2 (hydrogen atoms), and more preferably.
• a is 0 ⁇ a ⁇ 10, preferably 2 ⁇ a ⁇ 5, and more preferably 2 ⁇ a ⁇ 3.
• a exceeds 10
• the viscosity of the organohydrogenpolysiloxane becomes too low and the water repellency decreases.
• b is 0 ⁇ b ⁇ 100, preferably 0 ⁇ b ⁇ 50, and more preferably 0 ⁇ b ⁇ 30.
• b exceeds 100, the viscosity of the organohydrogenpolysiloxane becomes too high and emulsion stability deteriorates.
• c is 0 ⁇ c ⁇ 500, preferably 10 ⁇ c ⁇ 500, more preferably 20 ⁇ c ⁇ 200, even more preferably 30 ⁇ c ⁇ 100.
• c exceeds 500, the viscosity of the organohydrogenpolysiloxane becomes too high, resulting in poor emulsion stability.
• d exceeds 5
• the viscosity of the organohydrogenpolysiloxane becomes too low, resulting in a decrease in water repellency.
• e exceeds 5
• the viscosity of the organohydrogenpolysiloxane becomes too low, resulting in a decrease in water repellency. Note that 0 ⁇ a+b+c+d+e.
• the viscosity of component (A) at 25° C. is 5 to 1,000 mPa ⁇ s, preferably 5 to 800 mPa ⁇ s, more preferably 10 to 500 mPa ⁇ s, and even more preferably 10 to 100 mPa ⁇ s. If the viscosity is less than the above lower limit, the texture of the fibers will be poor. Moreover, when the above upper limit is exceeded, emulsion stability deteriorates.
• the viscosity is a value measured using a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.). Note that the rotor, rotation speed, and rotation time are appropriately selected according to the viscosity based on a conventional method.
• Examples of the component (A) include compounds represented by the following formulas. (a, b, c, d, and e are numbers that satisfy the following ranges: 0 ⁇ a ⁇ 10, 0 ⁇ b ⁇ 100, 0 ⁇ c ⁇ 500, 0 ⁇ d ⁇ 5, 0 ⁇ e ⁇ 5.)
• Component (B) is a (meth)acrylic polymer containing one or more structural units selected from the following (B-1) to (B-3), and is used alone or in combination of two or more. be able to.
• the (meth)acrylic polymer includes a polymer and a copolymer, and may be either a block (co)polymer or a random di(co)polymer.
• (meth)acrylic includes both acrylic and methacryl.
• R 4 to R 6 are each independently a group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group, and an aralkyl group, and R 7 and R 9 are each independently a hydrogen atom.
• R 8 is a group independently selected from a phenylene group and an alkyleneoxycarbonyl group having 1 to 11 carbon atoms
• R 10 is an alkyl group having 1 to 30 carbon atoms, a hydroxyalkyl group, and hydrogen.
• a group selected from atoms, and X is -Si-(CH 3 ) 3-m (OR x ) m is a hydrolyzable silyl group, (In the formula, R x is a group selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group, and an aryl group having an alkyl substituent and an aralkyl group, and m is a group having 1 to 3 carbon atoms. is an integer, and when m is 2 or 3, R x may be different from each other.) is a hydrolyzable silyl group represented by, n represents an integer of 3 to 500. ]
• R 4 to R 6 are each independently a group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group, and an aralkyl group, and more specifically, the alkyl group includes a methyl group, an ethyl group, , propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, alkyl group such as tridecane, chloromethyl group, chloropropyl group, bromoethyl group, etc.
• aryl group examples include a phenyl group, tolyl group, xylyl group, and naphthyl group.
• aralkyl group examples include benzyl group, phenylethyl group, and phenylpropyl group. These may be substituted. Among these, an alkyl group or an aryl group having 1 to 20 carbon atoms is preferred, and a methyl group is more preferred from the viewpoint of versatility.
• R 7 and R 9 are independently a hydrogen atom or a methyl group
• R 8 is independently a group selected from a phenylene group and an alkyleneoxycarbonyl group having 1 to 11 carbon atoms.
• R 8 is preferably an alkyleneoxycarbonyl group having 3 or 4 carbon atoms.
• R 10 is an alkyl group having 1 to 30 carbon atoms or a hydrogen atom, and examples thereof include linear or branched unsubstituted or substituted alkyl groups. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group. Examples include alkyl groups such as 2-hydroxyethyl groups, chloromethyl groups, chloropropyl groups, bromoethyl groups, and the like. Among these, an alkyl group having 1 to 20 carbon atoms or a hydrogen atom is preferred, and an alkyl group having 1 to 10 carbon atoms or a hydrogen atom is preferred.
• X is -Si-(CH 3 ) 3-m (OR x ) m
• R x is a group selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group, and an aryl group having an alkyl substituent and an aralkyl group
• m is a group having 1 to 3 carbon atoms. is an integer, and when m is 2 or 3, R x may be different from each other.
• It is a hydrolyzable silyl group represented by
• n is an integer from 3 to 500, preferably from 5 to 100, and more preferably from 10 to 50. If n is less than 3, the water resistance of the formed film will not be sufficient, while if it exceeds 500, the glass transition point of the resulting acrylic-silicone graft copolymer will be too low, resulting in insufficient strength. It becomes impossible to form a film with
• the structural units (B-1), (B-2) and (B-3) in component (B) are replaced by (B-1) and (B-3) in order to improve the texture during fiber processing. It is preferable that the selected structural unit is included. Among these, it is preferable to include a structural unit selected from (B-3).
• the amount of the structural unit (p+r) of (B-1) or (B-3) in component (B) is not particularly limited, but it is preferably 0.1 mol% or more in component (B), and Particularly preferred is .5 mol% or more.
• the upper limit is not particularly limited, but may be 100 mol% or 50 mol% or less.
• the structural unit (p) of (B-1) is preferably 0 to 5 mol%, more preferably 1 to 5 mol%, and even more preferably 1 to 3 mol%.
• the structural unit (r) of (B-3) is preferably 0.3 to 10 mol%, more preferably 0.5 to 5 mol%, in component (B).
• the structural units (q, s, t) of (B-2) are preferably 0 to 99.9 mol%, more preferably 50 to 99.5 mol%, and even more preferably 80 to 99.2 mol%.
• component (B) examples include the following. Note that the bonding order of each siloxane unit shown in parentheses is not limited to the following. (In the formula, p, q, r, s, and t represent the molar ratio of each structural unit in the polymer. n is the same as above.)
• the weight average molecular weight of component (B) is not particularly defined, but is preferably from 2,000 to 100,000, more preferably from 3,000 to 80,000, even more preferably from 5,000 to 60,000. If the molecular weight is less than 2,000, the durability of the film may be weakened, and if it is greater than 100,000, the feel of the fiber may deteriorate.
• the weight average molecular weight is a value calculated in terms of polystyrene by dissolving component (B) in toluene by GPC (gel permeation chromatography).
• Component (B) can be obtained, for example, by reacting an organopolysiloxane compound having a radically polymerizable group with a (meth)acrylic monomer, as described in JP-A No. 2007-107013.
• (meth)acrylic compounds represented by the general formula (B-2') A so-called macromonomer method is preferred, in which a system monomer is (co)polymerized with a silane having a radically polymerizable group represented by the general formula (B-3') in the presence of a radical polymerization initiator. By adjusting the monomers used, their amounts, etc., the desired (co)polymer can be obtained.
• the organopolysiloxane compound having a radically polymerizable group represented by the general formula (B-1') is, for example, an acryloxy group- or methacryloxy group-substituted chlorosilane compound represented by the following general formula (B-1'-1).
• a single-end reactive diorganopolysiloxane represented by the following formula (B-1'-2) can be obtained by subjecting it to a dehydrochloric acid reaction or a desalting reaction in accordance with a conventional method.
• One type can be used alone or two or more types can be used in appropriate combination. (In the formula, R 4 to R 8 and n are the same as above.)
• the (meth)acrylic monomer mainly composed of acrylate and/or methacrylate represented by general formula (B-2') means a compound having one radically polymerizable unsaturated bond in the molecule.
• Examples of the silane having a radically polymerizable group represented by the general formula (B-3') include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxymethyldiethoxysilane. , 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and the like. These can be used alone or in an appropriate combination of two or more.
• radical polymerization initiators examples include peroxides such as benzoyl peroxide, dicumyl peroxide, and t-butylperoxy-2-ethylhexylhexanoate; azo compounds such as azobisisobutyronitrile; This is carried out in the presence of a conventional radical polymerization initiator such as an inorganic peroxide such as potassium sulfate, sodium persulfate, or ammonium persulfate.
• peroxides such as benzoyl peroxide, dicumyl peroxide, and t-butylperoxy-2-ethylhexylhexanoate
• azo compounds such as azobisisobutyronitrile
• the amount of the radical polymerization initiator used may be the usual amount, preferably 0.01 to 5.00% by mass of the total amount of monomers involved in the copolymerization, and the amount of the radical polymerization initiator is preferably 0.01 to 5.00% by mass based on the amount of the total monomers involved in the copolymerization. It is selected appropriately depending on the degree of polymerization and the type of radical polymerization initiator.
• the copolymerization method in the present invention any one of a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method can be applied.
• organic solvent used when producing component (B) examples include aromatic hydrocarbon solvents such as toluene and xylene, hydrocarbon solvents such as hexane and octane, dibutyl ether, dioxane, etc. , ether solvents such as tetrahydrofuran, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone (MEK), alcohol solvents such as ethanol, isopropanol, and 1-butanol, chlorinated hydrocarbon solvents, etc. Can be mentioned.
• aromatic hydrocarbon solvents such as toluene and xylene
• hydrocarbon solvents such as hexane and octane
• dibutyl ether dioxane
• dioxane etc.
• ether solvents such as tetrahydrofuran
• ester solvents such as ethyl acetate and but
• the blending amount of component (B) is 5 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 30 to 75 parts by weight, and 40 to 60 parts by weight based on 100 parts by weight of component (A). More preferably, it is 15 to 50 parts by mass. If it is less than 5 parts by mass, the water repellency after washing will decrease, and if it exceeds 100 parts by mass, the texture of the fiber will deteriorate.
• the surfactant as component (C) is not particularly limited and includes, for example, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like. These can be used alone or in an appropriate combination of two or more.
• nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.
• anionic surfactants include alkyl sulfate salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, alkylbenzene sulfonates, and polyoxyethylene alkyl phenyl ethers.
• alkyldiphenyl ether disulfonate alkanesulfonate, N-acyl taurate, dialkyl sulfosuccinate, monoalkyl sulfosuccinate, polyoxyethylene alkyl ether sulfosuccinate, fatty acid salt, polyoxyethylene alkyl ether Examples include carboxylic acid salts, N-acylamino acid salts, monoalkyl phosphate ester salts, dialkyl phosphate ester salts, and polyoxyethylene alkyl ether phosphate ester salts.
• Cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylenealkyldimethylammonium salts, dipolyoxyethylenealkylmethylammonium salts, tripolyoxyethylenealkylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts. salts, monoalkylamine salts, monoalkylamide amine salts, and the like.
• amphoteric surfactants include alkyldimethylamine oxide, alkyldimethylcarboxybetaine, alkylamidopropyldimethylcarboxybetaine, alkylhydroxysulfobetaine, alkylcarboxymethylhydroxyethylimidazoliniumbetaine, and the like.
• nonionic surfactants and anionic surfactants are preferred, and nonionic surfactants are particularly preferred.
• HLB is not particularly limited, but preferably 9 to 17. Note that HLB measurement is based on the Griffin method.
• the blending amount of component (C) is 0.5 to 50 parts by mass, preferably 1.0 to 25 parts by mass, and more preferably 1.5 to 20 parts by mass, per 100 parts by mass of component (A). , 3 to 7 parts by mass is more preferable. If the amount of component (C) is too small, emulsification will be difficult, and if it is too large, water repellency will decrease.
• Component (D) is a condensation reaction catalyst for promoting the reaction between the hydrogen atoms directly bonded to the silicon atoms of component (A) and the reactive functional groups on the fibers.
• Component (D) can be used alone or in an appropriate combination of two or more.
• the condensation reaction catalyst include compounds of various metals such as tin, zinc, bismuth, titanium, zirconium, aluminum, iron, and lead.
• compounds of one or more metals selected from tin, zinc, bismuth, titanium, zirconium, and aluminum are preferred from the viewpoint of high catalytic activity and easy availability, and one metal compound selected from tin, zinc, and titanium is preferred. Compounds of the above metals are more preferred.
• the metal compound of component (D) is a salt and/or complex having the above-mentioned metal ion as a central element, preferably a carbonaceous compound having an alkyl group having 1 to 30 carbon atoms as a counter ion and/or a ligand. It has at least one selected from acids, ketones, esters, chloride ions, bromide ions, and iodide ions.
• examples of the alkyl group include a methyl group, an isopropyl group, a butyl group, a 2-ethylhexyl group, an octyl group, an isodecyl group, an isostearyl group, a decanyl group, and a cetyl group.
• component (D) examples include tin bis(2-ethylhexanoate), zinc bis(2-ethylhexanoate), zinc laurate, zinc acetate, zirconium acetate, zinc formate, and zinc bis(2-ethylhexanoate).
• the blending amount of component (D) is 0.1 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, and 10 to 40 parts by weight based on 100 parts by weight of component (A). parts by weight is more preferable, and 11 to 20 parts by weight is particularly preferable. If the amount of component (D) is too small, water repellency will decrease, and if it is too large, flexibility and texture will decrease.
• the water repellent composition of the present invention contains (E) water.
• the amount of water blended is 50 to 3,000 parts by weight, preferably 50 to 2,000 parts by weight, and more preferably 100 to 300 parts by weight, per 100 parts by weight of component (A).
• the fluorine compound is preferably less than 1 part by mass per 100 parts by mass of component (A). More preferably, the content of the fluorine compound is less than 0.5 parts by mass per 100 parts by mass of component (A), and even more preferably 0.1 parts by mass per 100 parts by mass of component (A). less than In particular, it is preferable not to contain a fluorine compound, but a trace amount of a fluorine compound may be unintentionally included as an impurity contained in the raw material.
• component (A) alone provides high initial water repellency, the water repellency decreases after washing.
• component (B) By using component (A) and component (B) together, it is possible to suppress a decrease in water repellency during washing, and it is possible to maintain high water repellency even after washing.
• component (B) is a film-forming type of polymer, it is believed that when treated on fibers, it forms a film on the surface and has the effect of preventing moisture from penetrating into the fibers.
• Component (B) alone cannot exhibit high water repellency; however, in contrast to a composition that exhibits high water repellency alone, such as component (A), a film-forming type such as component (B) It is believed that the addition of the composition made it possible to achieve high water repellency and washing durability.
• the water repellent composition of the present invention contains various thickeners, pigments, dyes, penetrants, antistatic agents, antifoaming agents, flame retardants, antibacterial agents, and preservatives to the extent that they do not impair the effects of the present invention.
• a crosslinking agent, an adhesion improver, and other silicone oils, silicone resins, acrylic resins, urethane resins, etc. can be appropriately blended.
• thickeners, pigments, dyes, penetrants, antistatic agents, antifoaming agents, flame retardants, antibacterial agents, preservatives, crosslinking agents, and adhesion improvers the blending amount is 100% of component (A).
• the amount can be 100 parts by mass or less, more preferably 50 parts by mass or less, and more preferably 30 parts by mass or less.
• the blending amount can be 300 parts by mass or less, and further 200 parts by mass or less, per 100 parts by mass of component (A). It is preferably 100 parts by mass or less, and more preferably 100 parts by mass or less.
• solvents can be used in the composition of the present invention, if necessary.
• the solvent include ether solvents such as dibutyl ether, dioxane, and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone (MEK), methanol, ethanol, 2-propanol, n-butanol, sec-butanol, and 2-ethyl- 1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3- Propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentane
• solvents may be used alone or in combination of two or more.
• the amount can be 200% by mass or less, preferably 100% by mass or less, and more preferably 50% by mass or less, based on the total amount of components (A) to (E).
• the method for preparing the water repellent composition of the present invention is not particularly limited, and may be according to conventionally known emulsion polymerization methods and phase inversion emulsification methods. Each component may be emulsified separately and mixed, or each component may be mixed and emulsified all at once. For example, an emulsion containing component (A) and an emulsion containing component (B) may be prepared separately and then mixed. Alternatively, components (A) and (B) may be mixed and emulsified. An emulsion containing both component (A) and component (B) may be prepared by doing so.
• the emulsifying machine is not particularly limited, and for example, a homomixer, a homogenizer, a colloid mill, a universal mixer, a combimix, a line mixer, etc. can be used.
• the type of the obtained emulsion is not particularly limited, and may be any type such as O/W type or W/O type.
• acids such as acetic acid, lactic acid, hydrochloric acid, sulfuric acid, and citric acid
• bases such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium acetate, and triethanolamine
• silicone oil, hydrocarbon oil, etc. can be used as a viscosity modifier.
• the water repellent composition of the present invention is used by treating the surface of various substrates such as fibers, paper, metals, wood, rubber, plastics, and glass.
• various conventionally known coating methods can be used, such as coating method, roll coating method, bar coating method, and brush coating method.
• the amount of the water repellent composition applied is not particularly limited, but it is usually an amount of 0.1 to 200 g/m 2 , particularly 1 to 100 g/m 2 as the water repellent composition.
• an organopolysiloxane film can be obtained by simply drying, and the drying can be carried out under conditions that allow water to evaporate, for 1 to 3 days at room temperature, or at 100 to 180°C when heated. Drying for about 1 to 30 minutes is sufficient.
• the water repellent composition of the present invention is useful as an active ingredient of a fiber treatment agent because the treated fiber surface has excellent water repellency.
• This water repellent composition may be used as a fiber treatment agent as it is, or may be appropriately blended into a fiber treatment agent, for example, in a range of 0.01 to 99% by mass.
• other components in the fiber treatment agent include textile agents such as anti-wrinkle agents, flame retardants, antistatic agents, and heat resistant agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, and rheology control agents. , curing accelerators, deodorants, antibacterial agents, etc.
• the fiber treatment agent may be diluted and used, and the amount of water repellent composition blended in the diluted fiber treatment agent solution for treating fibers is 0.01 to 10% by mass as solid content. Preferably, 0.1 to 7% by mass is more preferable.
• the water repellent composition and fiber treatment agent of the present invention can be applied not only to natural fibers such as cotton, silk, linen, wool, angora, and mohair, but also to synthetic fibers such as polyester, nylon, acrylic, urethane, and spandex, and synthetic fibers using these. All are also effective for textile products. There are no restrictions on its form or shape, and it is not limited to raw material forms such as staples, filaments, tows, threads, etc., but also various processed forms such as woven fabrics, knitted fabrics, stuffed cotton, non-woven fabrics, paper, sheets, and films. These materials can also be treated with the fiber treatment agent of the present invention.
• the water repellent composition and fiber treatment agent of the present invention can also be applied to base materials other than fibers.
• Substrates to which the water repellent composition and fiber treatment agent are applied include concrete, lightweight concrete, lightweight aerated concrete (ALC), mortar, various cement boards, gypsum boards, calcium silicate boards, bricks, and roof tiles. , tiles, stones, and other inorganic porous materials. It can also be used for walls made mainly of diatomaceous earth, clay, plaster, etc., and organic porous materials such as paper, wood, leather, etc.
• Example, Comparative Example The respective compositions obtained in the above production examples were blended in the amounts listed in the table below to obtain water repellent compositions of Examples and Comparative Examples. (indicates the amount of ingredients). The following evaluation tests were conducted on the obtained water repellent composition. The results are also listed in the table.
• the amount of the fluorine compound in the water repellent composition of the example was less than 1 part by mass based on 100 parts by mass of component (A).

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• Chemical & Material Sciences (AREA)
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• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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• 2023
  • 2023-08-03 WO PCT/JP2023/028421 patent/WO2024038771A1/ja not_active Ceased
  • 2023-08-03 JP JP2024541494A patent/JPWO2024038771A1/ja active Pending
  • 2023-08-16 TW TW112130749A patent/TW202419607A/zh unknown

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