Classifications

• • 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
  • 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
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
• • 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
  • D06M13/322—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 nitrogen
  • D06M13/395—Isocyanates
• • 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

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 compounds have traditionally 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. However, the range of application of fluorine compounds is limited because they are expensive and require treatment at high temperatures in order to exhibit high water repellency. In addition, 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.
• Patent Document 1 discloses a composition containing an acrylic-silicone graft polymer compound as a main component
• Patent Document 2 JP 2018-104866
• Patent Document 3 discloses a composition containing modified silica as a main component.
• Silicon 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 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.
• Patent Documents 1 to 3 do not describe water repellency after washing.
• JP2016-204565A Patent Document 4
• International Publication No. 2019/131456 Patent Document 5
• compositions containing amino-modified silicone as a silicon compound that are used as water repellents. It is stated that it can maintain water repellency even after repeated washing.
• amino-modified silicones are known to yellow when heated or stored for long periods of time, and water repellents containing amino-modified silicones have the problem that treated textile products may yellow. be.
• Patent No. 2960304 Japanese Patent Application Publication No. 2018-104866 Patent No. 6573548 JP2016-204565A International Publication No. 2019/131456
• the present invention provides a fiber treatment agent that has an excellent water repellency imparting effect, can impart good flexibility and texture to treated fibers, and includes the same.
• the purpose is to
• the present invention also provides a water repellent composition that can maintain good water repellency even after washing.
• composition containing the following components (A) to (E) imparts high water repellency to fibers as well as good flexibility and texture. We have discovered that this is possible, and have come up with the present invention.
• the water repellent composition of the present invention can impart high water repellency to fibers as well as good flexibility and texture.
• Component (A) of the present invention has the following average composition formula (1):
• 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 an organohydrogenpolysiloxane represented by the following formula and has a viscosity of 5 to 1,000 mPa ⁇ s at 25°C, and can be
• 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 10 ⁇ b ⁇ 70, and more preferably 20 ⁇ b ⁇ 50.
• 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 and emulsion stability deteriorates.
• 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.
• the viscosity of component (A) at 25° C. is 5 to 1,000 mPa ⁇ s, preferably 10 to 100 mPa ⁇ s.
• the viscosity is a value measured using a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.).
• BM type viscometer for example, manufactured by Tokyo Keiki Co., Ltd.
• 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 average composition formula. (In the formula, a to e are the same as above.)
• Component (B) of the present invention is (B) (b1) The following average composition formula (2) (In the formula, R 4 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms (excluding the group defined by R 5 and the phenyl group described later), R 5 is independently an alkenyl group having 2 to 6 carbon atoms, or an alkenyl group having 1 to 6 carbon atoms in which a portion of the hydrogen atoms bonded to the carbon atoms is substituted with a mercapto group, a vinyl group, an acryloxy group, or a methacryloxy group; is an alkyl group, R 6 is independently a phenyl group or a group defined for R 4 above, at least one R 6 is a phenyl group, and A monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, f, g, h and i
• Component (b1) is an organopolysiloxane represented by the average compositional formula (2) above, and can be used alone or in combination of two or more.
• R 4 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms (excluding the group defined by R 5 and the phenyl group described later).
• R 4 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
• R 4 examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, etc.
• Alkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, aryl group such as tolyl group, naphthyl group, alkenyl aryl group such as vinylphenyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group groups, alkenylaralkyl groups such as vinylbenzyl groups and vinylphenylpropyl groups, and some or all of the hydrogen atoms of these groups are halogen atoms such as fluorine, bromine, and chlorine, carboxyl groups, alkoxy groups, and alkenyloxy groups. , an amino group, and those substituted with alkyl or alkoxy.
• R 4 is preferably an unsubstituted alkyl group having 1 to 6 carbon atoms, more preferably a methyl group.
• R 5 is independently an alkenyl group having 2 to 6 carbon atoms, or an alkenyl group having 1 to 6 carbon atoms in which a portion of the hydrogen atoms bonded to the carbon atoms is substituted with a mercapto group, a vinyl group, an acryloxy group, or a methacryloxy group; is an alkyl group.
• a methyl group, an ethyl group, and a propyl group are preferable.
• R 6 are each independently a phenyl group or a group defined for R 4 above, and at least one R 6 is a phenyl group.
• X is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group.
• the unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms include the groups exemplified above for R 1 .
• the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, and tetradecyloxy group.
• a hydroxyl group, a methoxy group, an ethoxy group, a methyl group, a butyl group, and a phenyl group are preferable, and a hydroxyl group, a methoxy group, and an ethoxy group are more preferable.
• f, g, h and i are real numbers, and the formula 0.11 ⁇ f/(f+g+h+i) ⁇ 1, 0.00001 ⁇ g/(f+g+h+i) ⁇ 0.05, 0 ⁇ h/(f+g+h+i) ⁇ 0. 6, and 0.000001 ⁇ i/(f+g+h+i) ⁇ 0.24.
• f is a number that satisfies 0.11 ⁇ f/(f+g+h+i) ⁇ 1 (for example, 0.999999 or less), and preferably a number that satisfies 0.59 ⁇ f/(f+g+h+i) ⁇ 0.99998.
• g is a number satisfying 0.00001 ⁇ g/(f+g+h+i) ⁇ 0.05, and preferably a number satisfying 0.00001 ⁇ g/(f+g+h+i) ⁇ 0.01.
• h is a number satisfying 0 ⁇ h/(f+g+h+i) ⁇ 0.6, and preferably a number satisfying 0 ⁇ h/(f+g+h+i) ⁇ 0.30.
• i is a number satisfying 0.000001 ⁇ i/(f+g+h+i) ⁇ 0.24, and preferably a number satisfying 0.00001 ⁇ i/(f+g+h+i) ⁇ 0.1. If g exceeds 5% of the total of f to i, the tactile feel of the coating film will not improve and the antifouling properties will also deteriorate.
• h is the number of siloxane units having phenyl groups. The above range is preferable from the viewpoint of transparency and heat resistance.
• i exceeds 24% of the total of f to i, the weight average molecular weight becomes small and no improvement in tactile sensation is observed.
• the weight average molecular weight of the organopolysiloxane is preferably 5,000 or more and 500,000 or less, more preferably 8,000 or more and 450,000 or less, and 100,000 or more and 450,000 or less. is more preferable, and 150,000 or more and 400,000 or less are particularly preferable.
• the above weight average molecular weight can be calculated from the specific viscosity ⁇ sp (25° C.) of a toluene solution of organopolysiloxane having a concentration of 1 g/100 ml.
• ⁇ sp ( ⁇ / ⁇ 0)-1 ( ⁇ 0: viscosity of toluene, ⁇ : viscosity of solution)
• 20 g of the emulsion is mixed with 20 g of IPA (isopropyl alcohol), the emulsion is broken, the IPA is discarded, and the remaining rubbery organopolysiloxane is dried at 105° C.
• the organopolysiloxane (b1) is preferably used in the form of an emulsion, and a commercially available product may be used or it may be synthesized. When synthesized, it can be carried out by a known emulsion polymerization method, for example, a cyclic organosiloxane or ⁇ , ⁇ -dihydroxysiloxane oligomer that may have a fluorine atom, a (meth)acryloxy group, a carboxyl group, a hydroxyl group, an amino group, After emulsifying and dispersing ⁇ , ⁇ -dialkoxysiloxane oligomer, alkoxysilane, etc.
• a known emulsion polymerization method for example, a cyclic organosiloxane or ⁇ , ⁇ -dihydroxysiloxane oligomer that may have a fluorine atom, a (meth)acryloxy group, a carboxyl group, a
• R 7 (4-jk) R 8 l Si(OR 9 ) m (3)
• R 7 represents a monovalent organic group having a polymerizable double bond, particularly an alkyl group having 1 to 6 carbon atoms substituted with an acryloxy group or methacryloxy group.
• R 8 represents an alkyl group having 1 to 4 carbon atoms
• R9 is an alkyl group having 1 to 4 carbon atoms
• j is 2 to 3
• k is an integer of 0 to 1
• l+m 2 to 3.
• cyclic organosiloxane examples include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and 1,1-diethyl Hexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetramethyl Cyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane, 1,3,5,7-tetra(3-me
• silane coupling agent examples include ⁇ -(meth)acryloxypropyltrimethoxysilane, ⁇ -(meth)acryloxypropyltriethoxysilane, ⁇ -(meth)acryloxypropyltripropoxysilane, ⁇ -(meth) Acryloxypropyltriisopropoxysilane, ⁇ -(meth)acryloxypropyltributoxysilane, ⁇ -(meth)acryloxypropylmethyldimethoxysilane, ⁇ -(meth)acryloxypropylmethyldiethoxysilane, ⁇ -(meth) Acrylic silanes such as acryloxypropylmethyldipropoxysilane, ⁇ -(meth)acryloxypropylmethyldiisopropoxysilane, ⁇ -(meth)acryloxypropylmethyldibutoxysilane; ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ - Examples include mercaptosilanes such as
• a polymerizable group (R 5 ) is introduced into the organopolysiloxane.
• the (b2) (meth)acrylic acid ester monomer can be graft-polymerized onto the polymerizable group (R 5 ) of the (b1) organopolysiloxane.
• any known polymerization catalyst may be used.
• strong acids are preferred, and examples thereof include hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid.
• Preferred is dodecylbenzenesulfonic acid which has emulsifying ability.
• the amount of the acid catalyst used is preferably 0.01 to 10 parts by weight, more preferably 0.2 to 2 parts by weight, per 100 parts by weight of the cyclic organosiloxane.
• surfactants used in polymerization include anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acylamino acid salts, N-acyl taurine salts, aliphatic soaps, and alkyl phosphates. Among these, those that are easily soluble in water and do not have polyethylene oxide chains are preferred. N-acyl amino acid salts, N-acyl taurate salts, aliphatic soaps, and alkyl phosphates are more preferred, and sodium lauroylmethyltaurate, sodium myristoylmethyltaurate, and sodium lauryl sulfate are even more preferred.
• anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acylamino acid salts, N-acyl taurine salts, aliphatic soaps, and alkyl phosphates.
• anionic surfactants such as sodium lauryl sulfate, sodium laureth
• the amount of anionic surfactant used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the cyclic organosiloxane.
• the polymerization temperature is preferably 50 to 75°C, and the polymerization time is preferably 10 hours or more, more preferably 15 hours or more. Furthermore, it is preferable to age the polymer at 5 to 30°C for 10 hours or more after polymerization.
• the (b2) (meth)acrylic ester monomer includes acrylic esters and methacrylic esters, and includes acrylic esters, methacrylic esters, acrylic esters, and methacrylic esters.
• the proportion of methacrylic acid ester in component (b2) is preferably 50 mol% or more, more preferably 75 mol% or more, and even more preferably 90 mol% or more.
• the (meth)acrylic acid ester monomer is preferably a linear or branched alkyl ester, and may have a functional group such as an amide group, a vinyl group, a carboxyl group, or a hydroxyl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 to 3.
• Examples of (meth)acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. . One or more of these may be copolymerized. Among these, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate are preferred.
• the (meth)acrylic ester preferably has a glass transition temperature (hereinafter sometimes referred to as Tg) of 120°C or lower, more preferably 110°C or lower.
• the lower limit is preferably -50°C.
• component (b2) it is preferable to adjust component (b2) and carry out graft copolymerization so that the Tg of the resulting silicone-acrylic copolymer resin is 0° C. or higher, more preferably 5° C. or higher.
• Component (B) of the present invention is a silicone acrylic copolymer resin that is a copolymer of (b1) organopolysiloxane and (b2) (meth)acrylic acid ester monomer;
• An emulsion form of silicone acrylic copolymer resin obtained by emulsion graft polymerization of siloxane and (b2) (meth)acrylic acid ester monomer is preferable.
• the blending amount of component (b1) is 40 to 99% by mass, preferably 45 to 98% by mass, and 55 to 98% by mass in the copolymer (the total of components (b1) and (b2) is 100% by mass). is more preferable.
• the blending amount of component (b2) is 1 to 60% by weight, preferably 2 to 55% by weight, and more preferably 2 to 45% by weight.
• the graft copolymerization of the organopolysiloxane (b1) and the (meth)acrylic acid ester monomer (b2) may be carried out according to a conventionally known method, for example, using a radical initiator.
• a radical initiator include, but are not particularly limited to, persulfates such as potassium persulfate and ammonium persulfate, aqueous hydrogen persulfate, t-butyl hydroperoxide, and hydrogen peroxide.
• a redox system in which a reducing agent such as acidic sodium sulfite, Rongalite, L-ascorbic acid, tartaric acid, sugars, amines, etc. is used in combination can also be used.
• sodium lauryl sulfate, sodium laureth sulfate, N-acylamino acid salts, N-acyl taurine salts, aliphatic soaps, alkyl phosphates, etc. can be added as anionic surfactants.
• nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can also be added.
• a chain transfer agent can be added to adjust the molecular weight.
• the solid content (resin content) is preferably 35 to 50% by mass.
• the viscosity (25° C.) of the emulsion is preferably 500 mPa ⁇ s or less, more preferably 20 to 300 mPa ⁇ s. Viscosity can be measured with a rotational viscometer.
• the average particle diameter of the emulsion particles is preferably 1,000 nm or less, more preferably 100 to 500 nm, and even more preferably 150 to 350 nm. If the average particle size is too large, whitening will occur, and if the average particle size is too small, there will be a problem of reduced dispersibility.
• the particle size of the resin emulsion is measured using an electron microscope, for example, JEM-2100TM manufactured by JEOL.
• the glass transition temperature Tg of the silicone acrylic copolymer resin is preferably 0°C or higher, more preferably 5°C or higher.
• the glass transition temperature (hereinafter sometimes referred to as Tg) can be measured using a flow tester after drying the emulsion.
• the blending amount of component (B) is 5 to 100 parts by mass, preferably 10 to 80 parts by mass, more preferably 30 to 75 parts by mass, and further 40 to 70 parts by mass, per 100 parts by mass of component (A). preferable. 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) of the present invention is not particularly limited, and examples include 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.
• the HLB of the surfactant of the present invention is preferably 8 to 20. Note that HLB measurement is based on the Griffin method.
• 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.
• Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylenealkyldimethylammonium salts, dipolyoxyethylenealkylmethylammonium salts, tripolyoxyethylenealkylammonium salts, alkylbenzyldimethylammonium salts, Examples include alkylpyridinium salts, monoalkylamine salts, monoalkylamide amine salts, and the like.
• amphoteric surfactant examples include alkyldimethylamine oxide, alkyldimethylcarboxybetaine, alkylamidopropyldimethylcarboxybetaine, alkylhydroxysulfobetaine, alkylcarboxymethylhydroxyethylimidazoliniumbetaine, and the like.
• 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). , more preferably 1.5 to 10 parts by mass. 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) of the present invention is a condensation reaction catalyst for promoting the reaction between the hydrogen atom directly bonded to the silicon atom of component (A) and the reactive functional group on the fiber.
• 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. From the viewpoint of environmental impact, compounds of one or more metals selected from zinc and titanium 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 5 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 15 to 70 parts by weight, and 20 to 60 parts by weight based on 100 parts by weight of component (A). More preferred. 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 component (E) of the present invention is 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 70 to 500 parts by weight, per 100 parts by weight of component (A).
• the water repellent composition of the present invention preferably contains component (F): a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule.
• component (F) is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule, and known compounds can be used.
• Component (F) can be used alone or in combination of two or more.
• tolylene diisocyanate diphenylmethane diisocyanate, m-xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-m-xylylene diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene -1,5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene-1,6-diisocyanate, lysine diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatemethyl)-cyclohexane, 4,4, - It is a polymer of various diisocyanates such as dicyclohexylmethane diisocyanate, and includes polyisocyanates having an isocyanurate structure made of these.
• various diisocyanates such as those mentioned above, 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-pentanediol, 2-methyl-2,3 -butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2 -Ethyl-hexanediol, 1,2-octanediol, 1,2-decan
• Examples include polyisocyanates having a biuret structure obtained by reacting the above diisocyanates, and polyisocyanates having an isocyanurate structure obtained by cyclizing and trimerizing the above diisocyanates. It is also possible to use polyisocyanates obtained by reacting various polyisocyanates as described above with various polyols as described above.
• blocked isocyanate compounds in which isocyanate groups are blocked with a blocking agent can also be used.
• the blocked isocyanate compound is not particularly limited either, and known ones can be used.
• blocked polyisocyanates can be prepared by reacting various known polyisocyanate compounds with various known blocking agents. Examples of blocking agents include alcohol compounds, alkylphenol compounds, phenol compounds, active ethylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, urea compounds, oxime compounds, and amine compounds. , imide compounds, pyrazole compounds, and the like.
• the amount of component (F) to be blended is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and even more preferably 10 to 40 parts by weight based on 100 parts by weight of component (A).
• the fluorine compound is preferably less than 1 part by weight, more preferably less than 0.5 part by weight, and less than 0.1 part by weight based on 100 parts by weight of component (A). More preferred. 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.
• the amino-modified silicone is preferably less than 10 parts by mass, more preferably less than 5 parts by mass, and even more preferably less than 1 part by mass based on 100 parts by mass of component (A).
• the amount of amino-modified silicone is more than the above amount, the treated textile products and base materials tend to yellow.
• the water repellent composition of the present invention contains a solvent, a thickener, a pigment, a dye, a penetrant, an antistatic agent, an antifoaming agent, a flame retardant, an antibacterial agent, and a preservative to the extent that the effects of the present invention are not impaired.
• a crosslinking agent, an adhesion improver, and other silicone oils, silicone resins, acrylic resins, urethane resins, etc. can be appropriately blended.
• the total amount of component (A) is 100%.
• the amount can be 100 parts by mass or less, preferably 50 parts by mass or less.
• the blending amount can be 300 parts by mass or less, and further 200 parts by mass or less, based on 100 parts by mass of component (A). is preferred.
• the solvent examples 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-pentanediol, 2 -Methyl-2,3-butane
• 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 together. 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 emulsifier is not particularly limited, and for example, a homomixer, homogenizer, colloid mill, universal mixer, combimix, 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 to be applied is not particularly limited, but the amount of the water repellent composition is usually 0.1 to 200 g/m 2 , preferably 1 to 100 g/m 2 .
• an organopolysiloxane film can be obtained by simply drying, and this drying can be done under conditions that allow the water to evaporate, for 1 to 3 days at room temperature, or at 100 to 180°C when heated. Drying takes about 1 to 30 minutes.
• 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.
• Nonion K-204 1.2 parts by mass
• Nonion K-230 0.3 parts by mass
• Ion-exchanged water 38.5 parts by mass was mixed using a homomixer to emulsify and disperse, and then high-pressure treatment was performed using a high-pressure homogenizer under conditions of 30 MPa to form a silicone emulsion composition (I-1). ) was obtained.
• the emulsion was transferred to a 2 L glass flask equipped with a stirrer, a thermometer, and a reflux condenser, and a polymerization reaction was carried out at 55° C. for 24 hours. Thereafter, the mixture was aged at 15° C. for 24 hours, and then neutralized to near neutrality with 12 g of a 10% aqueous sodium carbonate solution.
• the structure of the organopolysiloxane obtained by the above polymerization reaction was represented by the following formula (b1-1), and the Mw (weight average molecular weight, measurement method was as described above) was 250,000.
• R 5 is a ⁇ -methacryloxypropyl group
• X is a hydroxyl group or an ethoxy group.
• MMA methyl methacrylate
• the emulsion was transferred to a 2 L glass flask equipped with a stirrer, a thermometer, and a reflux condenser, and the polymerization reaction was carried out at 55°C for 24 hours. After aging at 5°C for 24 hours, the emulsion was added with 12 g of a 10% aqueous sodium carbonate solution. Neutralized to near neutrality.
• the structure of the organopolysiloxane obtained by the above polymerization reaction was represented by the following formula (b1-2), and the Mw (weight average molecular weight, measurement method as described above) was 400,000.
• R 5 is a ⁇ -methacryloxypropyl group
• X is a hydroxyl group or an ethoxy group.
• MMA methyl methacrylate
• the emulsion was transferred to a 2 L glass flask equipped with a stirrer, a thermometer, and a reflux condenser, and the polymerization reaction was carried out at 55°C for 24 hours. After aging at 5°C for 24 hours, the emulsion was added with 12 g of a 10% aqueous sodium carbonate solution. Neutralized to near neutrality.
• the structure of the organopolysiloxane obtained by the above polymerization reaction was represented by the above formula (b1-2), and the Mw (weight average molecular weight) was 400,000.
• R 5 is a ⁇ -methacryloxypropyl group
• X is a hydroxyl group or an ethoxy group.
• the emulsion was transferred to a 2 L glass flask equipped with a stirrer, a thermometer, and a reflux condenser, and the polymerization reaction was carried out at 55°C for 24 hours. After aging at 5°C for 24 hours, the emulsion was added with 12 g of a 10% aqueous sodium carbonate solution. Neutralized to near neutrality.
• the structure of the organopolysiloxane obtained by the above polymerization reaction was represented by the above formula (b1-2), and the Mw (weight average molecular weight) was 250,000.
• R 5 is a ⁇ -methacryloxypropyl group
• X is a hydroxyl group or an ethoxy group.
• composition and physical properties of the silicone acrylic copolymer resin emulsion obtained in the above production example are summarized below.
• Example, Comparative Example The respective compositions obtained in the above production examples were blended in the amounts shown in Tables 2 and 3 below to obtain water repellent compositions of Examples and Comparative Examples. Tables 4 and 5 show the amount of each component relative to 100 parts by mass of component (A) for each formulation. The following evaluation tests were conducted on the obtained water repellent composition. The results are also listed in the table. Note that "%" in the composition is mass %.
• Results are shown for cotton broadcloth, polyester/cotton broadcloth (65%/35%), and polyester taffeta cloth.
• Water Repellency Ion-exchanged water was added to the above water repellent composition, stirred, and diluted to contain component (A) at 3% to prepare a test solution.
• a cotton broadcloth, a polyester/cotton broadcloth (65%/35%), a polyester taffeta cloth, and a nylon taffeta cloth were immersed in this test solution for 10 seconds, and then squeezed using a roll at a squeezing rate of 100% at 150°C.
• the fabric was dried for 3 minutes to prepare a treated fabric for evaluation of flexibility. Thereafter, the treated fabric was washed 20 times in a washing machine in accordance with JIS L0217 103.
• the water repellent composition of the present invention has an excellent effect of imparting water repellency, and the treated fabric has good flexibility. Furthermore, the water repellent composition of the present invention maintains high water repellency even after washing.
• the water repellent composition of the present invention has an excellent effect of imparting water repellency, provides good flexibility to treated fabrics, and is capable of maintaining high water repellency even after washing. Furthermore, since the content of fluorine compounds is low, the load on the environment is low.

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• 2023
  • 2023-08-04 JP JP2024540438A patent/JPWO2024034530A1/ja active Pending
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