WO2020003971A1 - シリコーン組成物及びそれを用いた繊維処理剤 - Google Patents
シリコーン組成物及びそれを用いた繊維処理剤 Download PDFInfo
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- WO2020003971A1 WO2020003971A1 PCT/JP2019/022696 JP2019022696W WO2020003971A1 WO 2020003971 A1 WO2020003971 A1 WO 2020003971A1 JP 2019022696 W JP2019022696 W JP 2019022696W WO 2020003971 A1 WO2020003971 A1 WO 2020003971A1
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- 0 CC(*C(C)(C)C(C)*C(C)(C)OC)*N(*)* Chemical compound CC(*C(C)(C)C(C)*C(C)(C)OC)*N(*)* 0.000 description 6
- RICKMFQXMYMBNY-UHFFFAOYSA-N CC(C(C)(C)N)O Chemical compound CC(C(C)(C)N)O RICKMFQXMYMBNY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- 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
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- 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
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- 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
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- 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
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
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- 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
- D06M15/65—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Definitions
- the present invention relates to a water-dispersible silicone composition. More specifically, the present invention relates to a silicone composition that imparts high water absorption to fibers, and a fiber treatment agent containing the composition.
- fibers treated with a treating agent containing polysiloxane as a main component exhibit water repellency. Even fibers that originally have water absorbency exhibit hydrophobicity after being treated with polysiloxane, and, for example, when used in clothing, there is also a drawback that sweat absorption during sweating is almost lost.
- studies have been made to impart both flexibility and water absorption to the fiber. For example, the water absorption is improved by including an aminoalkyl group and a polyoxyalkylene group in the same polysiloxane molecule, but the flexibility and smoothness are greatly reduced by including the polyoxyalkylene group. There was a disadvantage.
- block copolymers having alternating siloxane and polyoxyalkylene are also used in the art (Japanese Patent No. 3859723, Japanese Patent Application Laid-Open No. 2004-528412: Patent Documents 3 and 4).
- the present invention has been made in view of the above-mentioned problems of the prior art, and has excellent water dispersibility, and a silicone composition showing a water absorbency on the fiber surface after the treatment. It is an object of the present invention to provide a water-dispersible silicone composition capable of maintaining the above condition, and a fiber treating agent containing the silicone composition.
- the present inventor has found that (A) a copolymer comprising a repeating unit of a polysiloxane and a polyalkylene oxide and (B) a polyether-modified silicone and / or (C) an organic acid. It has been found that the contained silicone composition has high water dispersibility. Further, they have found that a fiber treating agent containing the composition can impart good flexibility and water absorbability to the fiber, and exhibit higher washing durability, and have accomplished the present invention.
- (A1) a nitrogen atom-containing organopolysiloxane represented by the following general formula (1-1) and a polyoxyalkylene group-containing epoxy compound represented by the following general formula (2-1) or (2-2)
- R 1 is independently an alkyl group having 1 to 6 carbon atoms or a phenyl group
- R 2 is independently R 1 , an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group
- R 3 is each other R 4 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, provided that at least one of R 4 bonded to each nitrogen atom is hydrogen.
- R 5 is independently a divalent organic group, a is an integer of 1 to 1,000, b is an integer of 0 to 100, c is an integer of 0 to 100, b + c is an integer of 1 to 100.)
- B a polyether-modified silicone represented by the following general formula (4): 1 to 50 parts by mass,
- R 6 is independently a phenyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group
- R 7 is independently a formula —C g H 2g O (C a monovalent organic group represented by 2 H 4 O) h (C 3 H 6 O) i R 9,
- R 8 is R 6 or R 7 independently of one another,
- R 9 is a hydrogen atom, a carbon number 1 E is an integer of 0 to 100, f is an integer of 0 to 100, e + f is an integer of 0 to 200, and g is an integer of 2 to 5
- (C) Organic acid: 0.1 to 20 parts by mass. [2].
- (A2) An epoxy group-containing organopolysiloxane represented by the following general formula (1-2) or (1-3) and a polyoxyalkylene group-containing amine compound represented by the following general formula (2-3)
- R 1 is independently an alkyl group having 1 to 6 carbon atoms or a phenyl group
- R 2 is independently R 1 , an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group
- R 3 is each other R 4 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, provided that at least one of R 4
- R 5 is independently a divalent organic group, a is an integer of 1 to 1,000, b is an integer of 0 to 100, c is an integer of 0 to 100, b + c is an integer of 1 to 100.)
- B a polyether-modified silicone represented by the following general formula (4): 1 to 50 parts by mass,
- R 6 is independently a phenyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group
- R 7 is independently a formula —C g H 2g O (C a monovalent organic group represented by 2 H 4 O) h (C 3 H 6 O) i R 9,
- R 8 is R 6 or R 7 independently of one another,
- R 9 is a hydrogen atom, a carbon number 1 E is an integer of 0 to 100, f is an integer of 0 to 100, e + f is an integer of 0 to 200, and g is an integer of 2 to 5
- (C) Organic acid: 0.1 to 20 parts by mass. [3].
- a fiber treating agent comprising the silicone composition according to any one of [1] to [3]. [5].
- the silicone composition of the present invention has excellent water dispersibility and can impart high water absorption to the fiber surface. Furthermore, the fiber treating agent using the silicone composition of the present invention has excellent washing durability and can maintain good water absorption of the fiber surface even after the washing treatment.
- the silicone composition of the present invention contains (A) a copolymer comprising a repeating unit of a polysiloxane and a polyalkylene oxide, (B) a polyether-modified silicone, and / or (C) an organic acid.
- Component (A) As the copolymer comprising the repeating unit of the polysiloxane and the polyalkylene oxide as the component (A), the following component (A1) or (A2) is used.
- the component (A1) comprises a nitrogen atom-containing organopolysiloxane represented by the following general formula (1-1) and a polyoxyalkylene group-containing epoxy represented by the following general formula (2-1) or (2-2). It is a copolymer having a siloxane group and a polyoxyalkylene group in the molecule, obtained by reacting a compound.
- R 1 is independently an alkyl group having 1 to 6 carbon atoms or a phenyl group
- R 2 is independently R 1 , an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group
- R 3 is each other
- R 4 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, provided that at least one of R 4 bonded to each nitrogen atom is hydrogen.
- R 5 is independently a divalent organic group, a is an integer of 1 to 1,000, b is an integer of 0 to 100, c is an integer of 0 to 100, b + c is an integer of 1 to 100.
- the component (A2) includes an epoxy group-containing organopolysiloxane represented by the following general formula (1-2) or (1-3) and a polyoxyalkylene group-containing amine represented by the following general formula (2-3) It is a copolymer having a siloxane group and a polyoxyalkylene group in the molecule, obtained by reacting a compound. (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , a, b, c, b + c are the same as described above.)
- R 1 is independently an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or a phenyl group.
- Group preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, particularly preferably a methyl group or a phenyl group.
- R 2 is independently R 1 , an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or the like having 1 to 6 carbon atoms, or a hydroxyl group. And is preferably R 1 , an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group, and particularly preferably R 1 , a methoxy group, an ethoxy group or a hydroxyl group.
- R 3 is independently a divalent organic group.
- the divalent organic group represented by R 3 as long as it has at least one carbon atom, it may contain a nitrogen atom, may have a hydroxyl group, and may have an ether bond. Is also good.
- R 3 include a group represented by the following formula. (Wherein, R 10 is a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, and R 11 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms.
- a hydrocarbon group, and k is an integer of 0 to 4, preferably 0 or 1.
- the divalent hydrocarbon group having 1 to 10 carbon atoms for R 10 for example, a methylene group, an ethylene group, a propylene group (a trimethylene group, a methylethylene group), a butylene group (a tetramethylene group, a methylpropylene group) And an alkylene group such as a hexamethylene group and an octamethylene group; an arylene group such as a phenylene group; a combination of two or more of these groups (such as an alkylene arylene group).
- R 11 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms.
- Examples of the monovalent hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group. And the like.
- R 3 is more preferably an ethylene group, a trimethylene group, a methylethylene group, or —CH 2 CH 2 CH 2 —NH—CH 2 CH 2 —.
- R 4 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl.
- a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
- at least one of R 4 bonded to the nitrogen atom is a hydrogen atom, and each has an NH group at both ends of the molecular chain.
- R 5 is a divalent organic group, and preferably has a carbon number which may be interposed by an oxygen atom. It is a divalent hydrocarbon group having 1 to 10 and more preferably a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom interposed.
- R 5 examples include alkylene groups such as a methylene group, an ethylene group, a propylene group (a trimethylene group, a methylethylene group), a butylene group (a tetramethylene group, a methylpropylene group), a hexamethylene group, and an octamethylene group;
- An arylene group such as a phenylene group, a combination of two or more of these groups (such as an alkylene arylene group), —CH 2 CH 2 —O—CH 2 CH 2 —, —CH 2 CH 2 CH 2 —O—CH 2 —, —CH (CH 3 ) CH 2 —O—CH (CH 3 ) CH 2 — and the like.
- R 5 is particularly preferably a methylene group, an ethylene group, a trimethylene group, or —CH 2 CH 2 CH 2 —O—CH 2 —.
- a is an integer of 1 to 1,000, preferably an integer of 5 to 500, particularly preferably 10 to 300. Is an integer. When a is 0, the texture imparting ability to the fiber when used as a softener is poor, and when it is more than 1,000, the dispersibility in water decreases.
- b is an integer of 0 to 100
- c is an integer of 0 to 100
- b + c is an integer of 1 to 100.
- b is an integer from 1 to 70
- c is an integer from 0 to 50
- b + c is an integer from 1 to 70.
- b is an integer of 1 to 50
- c is an integer of 0 to 30
- b + c is an integer of 3 to 50.
- nitrogen-containing organopolysiloxane represented by the formula (1-1) include, but are not limited to, the following. (In the formula, a is the same as described above.)
- polyoxyalkylene group-containing epoxy compound represented by the formula (2-1) include, but are not limited to, the following. (Where b and c are the same as above)
- polyoxyalkylene group-containing epoxy compound represented by the formula (2-2) include, but are not limited to, the following. (Where b and c are the same as above)
- epoxy group-containing organopolysiloxane represented by the formula (1-2) include, but are not limited to, the following. (In the formula, a is the same as described above.)
- epoxy group-containing organopolysiloxane represented by the formula (1-3) include, but are not limited to, the following. (In the formula, a is the same as described above.)
- polyoxyalkylene group-containing amine compound represented by the formula (2-3) include, but are not limited to, the following. (Where b and c are the same as above)
- component (A1) examples include those represented by the following formulas, but are not limited thereto. (In the formula, a, b, and c are the same as above, and n is 1 to 100.)
- component (A2) include those represented by the following formulas, but are not limited thereto. (In the formula, a, b, and c are the same as above, and n is 1 to 100.)
- the copolymer of the component (A) may be manufactured by a known method.
- the method for producing the copolymer of the component (A1) includes a nitrogen atom-containing organopolysiloxane represented by the formula (1-1) and a polyoxy compound represented by the formula (2-1) or (2-2). It can be produced by heating an alkylene group-containing epoxy compound in an organic solvent to react an amino group in a nitrogen atom-containing organopolysiloxane with an epoxy group in a polyoxyalkylene group-containing epoxy compound.
- the method for producing the copolymer of the component (A2) includes an epoxy group-containing organopolysiloxane represented by the formula (1-2) or (1-3) and a polyoxy compound represented by the formula (2-3). It can be produced by heating an alkylene group-containing amine compound in an organic solvent to react an amino group in the polyoxyalkylene group-containing amine compound with an epoxy group in the epoxy group-containing organopolysiloxane.
- the amino group is a —N (R 4 ) 2 group, ie, a —NH 2 group or a —NHR 4 ′ group (R 4 ′ is a monovalent hydrocarbon group having 1 to 6 carbon atoms).
- a nitrogen atom-containing organopolysiloxane represented by the formula (1-1) and a polyoxyalkylene group-containing organopolysiloxane represented by the formula (2-1) or (2-2) are provided.
- the compounding ratio when reacting with the epoxy compound is represented by the formula (2-1) or (2-2) with respect to 1 mol of the amino group in the nitrogen-containing organopolysiloxane represented by the formula (1-1).
- the amount of the epoxy group in the represented polyoxyalkylene group-containing epoxy compound is preferably 0.67 to 1.5 mol, more preferably 0.8 to 1.25 mol.
- the amount of the polyoxyalkylene group-containing epoxy compound represented by the formula (2-1) or (2-2) is too small, the water dispersibility may decrease, and gelation may occur during the reaction. If the amount of the polyoxyalkylene group-containing epoxy compound represented by the formula (2-1) or (2-2) is too large, gelation may occur during the reaction.
- an epoxy group-containing organopolysiloxane represented by the formula (1-2) or (1-3) and a polyoxyalkylene group-containing compound represented by the formula (2-3) The compounding ratio when reacting with the amine compound is the formula (1-2) or (1-3) based on 1 mol of the amino group in the polyoxyalkylene group-containing amine compound represented by the formula (2-3).
- the amount of the epoxy group in the epoxy group-containing organopolysiloxane represented by the formula is preferably from 0.67 to 1.5 mol, more preferably from 0.8 to 1.25 mol.
- the amount of the polyoxyalkylene group-containing amine compound represented by the formula (2-3) is too small, the water dispersibility may decrease, and gelation may occur during the reaction. If the amount of the polyoxyalkylene group-containing amine compound represented by the formula (2-3) is too large, gelation may occur during the reaction.
- the organic solvent used in the above reaction is not particularly limited, but examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, hydrocarbon solvents such as hexane and octane, dibutyl ether, dioxane, and tetrahydrofuran (THF).
- Ether solvents 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, and chlorinated hydrocarbon solvents.
- alcohol solvents having a high reaction rate improving effect are preferable.
- the amount of the organic solvent used is not particularly limited, but when producing the copolymer of the component (A1), the nitrogen atom-containing organopolysiloxane represented by the formula (1-1) and the compound represented by the formula (2-1) or (2)
- the amount is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, based on 100 parts by mass in total with the polyoxyalkylene group-containing epoxy compound represented by -2).
- an epoxy group-containing organopolysiloxane represented by the formula (1-2) or (1-3) and a polyoxyalkylene represented by the formula (2-3) is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, per 100 parts by mass in total with the group-containing amine compound.
- the reaction temperature is not particularly limited, but is preferably in the range of 50 to 120 ° C, particularly 70 to 110 ° C. If the temperature is lower than 50 ° C., the reaction rate may decrease. If the temperature exceeds 120 ° C., the possibility of coloring increases.
- the reaction time is not particularly limited, but is preferably 1 to 10 hours, particularly preferably 2 to 8 hours.
- the molecular weight of the obtained copolymer of the component (A) is preferably from 1,500 to 150,000, more preferably from 2,000 to 50,000. If the molecular weight is too small, the effect of imparting flexibility to the fiber may decrease, and if it is too large, the water dispersibility may decrease. In the present invention, the molecular weight is the number average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) analysis using THF as a developing solvent (the same applies hereinafter).
- GPC gel permeation chromatography
- the thus obtained copolymer of the component (A) can be added to the composition as an organic solvent solution without removing the organic solvent.
- the component (B) is a polyether-modified silicone represented by the following general formula (4).
- the component (B) can be used alone or in an appropriate combination of two or more.
- R 6 is independently a phenyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group
- R 7 is independently a formula —C g H 2g O (C a monovalent organic group represented by 2 H 4 O) h (C 3 H 6 O) i
- R 8 is R 6 or R 7 independently of one another
- R 9 is a hydrogen atom
- a carbon number 1 E is an integer of 0 to 100
- f is an integer of 0 to 100
- e + f is an integer of 0 to 200
- g is an integer of 2 to 5
- H is an integer of 1 to 40
- i is an integer of 0 to 40.
- f 0, at least one of R 8 is R 7.
- R 6 is independently a phenyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group or a hydroxyl group having 1 to 6 carbon atoms, and specific examples of R 6 include a methyl group and an ethyl group.
- R 6 include a methyl group and an ethyl group.
- R 7 is independently a monovalent organic group represented by the formula —C g H 2g O (C 2 H 4 O) h (C 3 H 6 O) i R 9. .
- R 9 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an acetyl group. Specific examples of R 9 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like. It is an alkyl group or an acetyl group.
- g is an integer of 2 to 5, preferably 2 to 4
- h is an integer of 1 to 40, preferably 1 to 20
- i is an integer of 0 to 40, preferably 0 to 40. It is an integer of 20.
- e is an integer of 0 to 100, preferably an integer of 0 to 50, and more preferably an integer of 0 to 30.
- f is an integer of 0 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 30.
- e + f is an integer of 0 to 200, preferably an integer of 1 to 100, and more preferably an integer of 1 to 60.
- R 8 is R 7
- 1 to 10 preferably 1 to 10, R 7 in the formula (4) It is preferable to have five.
- component (B) examples include the following. (In the formula, e ′ and f ′ are each an integer of 1 to 100, h is the same as described above, and i ′ is an integer of 1 to 40.)
- the compounding amount is 1 to 50 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the component (A).
- the component (B) is too small, the water absorption of the fiber surface becomes insufficient, and when the component (B) is too large, the stability of the composition is reduced.
- the effects of the component (B) of the present invention are considered as follows. Since the copolymer of the component (A) contains polysiloxane as a main component, it has an excellent effect of imparting flexibility to fibers. In addition, even if the component (A) is used alone, the effect of imparting water absorption to fibers is expected due to the polyalkylene oxide contained in the molecule, but the component (A) alone has poor water dispersibility.
- the component (B) has a high affinity for the component (A) and a high affinity for water, and thus has an effect like an emulsifier, and can improve the water dispersibility of the component (A). it is conceivable that.
- the component (C) is an organic acid. These can be used alone or in combination of two or more. Specific examples include monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, aromatic carboxylic acids, and acidic amino acids.
- monocarboxylic acids such as acetic acid, propionic acid and caprylic acid
- dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid and fumaric acid
- glycolic acid lactic acid, hydroxyacrylic acid
- Hydroxycarboxylic acids such as glyceric acid, malic acid, tartaric acid and citric acid
- aromatic carboxylic acids selected from benzoic acid, salicylic acid and phthalic acid
- acidic amino acids such as glutamic acid and aspartic acid.
- the compounding amount is 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass based on 100 parts by mass of the component (A). More preferred. If the amount of the component (C) is too small, the dispersibility in water may be insufficient. If the amount is too large, the stability of the composition may be reduced.
- the effect of the component (C) is considered as follows. It is considered that by adding the organic acid as the component (C), the amino group contained in the component (A) is partially cationized and the dispersibility in water is improved. It is considered that by partially cationizing the amino group of the component (A), the hydrophilicity of the component remaining on the treated cloth is improved, and the water absorption of the treated cloth is improved.
- the silicone composition of the present invention contains both the component (B) and the component (C), even if the component (B) and the component (C) are mixed with the component (A). However, it is preferable to mix both the component (B) and the component (C).
- the silicone composition of the present invention can be prepared by uniformly mixing the above component (A) with the component (B) and / or the component (C) according to a conventional method.
- the silicone composition of the present invention can be suitably used for a fiber treatment agent.
- the fiber treating agent containing the silicone composition of the present invention those obtained by dissolving the above silicone composition in an organic solvent, those dispersed in water or nonionic, anionic, cationic and amphoteric surfactants An emulsified product using an emulsifier such as the above is preferable.
- the amount of the silicone composition (component (A) and component (B) and / or component (C)) in the fiber treatment agent is 0.01 to 10% by mass, particularly 0.1
- the amount is preferably from 5 to 5% by mass, particularly preferably from 0.5 to 3% by mass. If the amount of the silicone composition is too small, the effect of imparting flexibility to the fibers may be reduced, and if the amount is too large, the yellowing of the fibers may be likely to progress.
- the fiber treatment agent of the present invention can contain (D) water.
- D When water is added, the amount is 10 to 10,000 parts by weight, preferably 20 to 6,000 parts by weight, based on 100 parts by weight of the silicone composition.
- solvents can be used for the fiber treatment agent of the present invention as needed.
- the solvent include ether solvents such as dibutyl ether, dioxane and THF, ketone solvents such as acetone and MEK, methanol, ethanol, 2-propanol, n-butanol, sec-butanol and 2-ethyl-1-hexanol.
- the amount of the organic solvent used is not particularly limited, but is preferably from 2,000 to 200,000 parts by mass, particularly preferably from 10,000 to 100,000 parts by mass, per 100 parts by mass of the silicone composition. .
- the emulsifier used when the fiber treating agent of the present invention is formed into an emulsion is not particularly limited.
- nonionic (nonionic) surfactants include ethoxylated higher alcohols, ethoxylated alkylphenols, and polyhydric alcohols. Examples thereof include alcohol fatty acid esters, ethoxylated polyhydric alcohol fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid amides, sorbitol, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, and sucrose fatty acid esters, and the HLB thereof is in the range of 5 to 20. And particularly preferably within the range of 10 to 16.
- anionic surfactants include higher alcohol sulfates, alkyl phenyl ether sulfates, alkyl benzene sulfonates, higher alcohol phosphates, ethoxylated higher alcohol sulfates, and ethoxylated alkyl phenyl ethers. Sulfate, ethoxylated higher alcohol phosphate and the like.
- the cationic surfactant include alkyltrimethylammonium chloride, alkylamine hydrochloride, coconutamine acetate, alkylamine acetate, alkylbenzenedimethylammonium chloride, and the like.
- amphoteric surfactants include N-acylamidopropyl-N, N-dimethylammoniobetaines, N-acylamidopropyl-N, N′-dimethyl-N′- ⁇ -hydroxypropylammoniobetaines Etc. are exemplified.
- the amount of the emulsifier used is preferably 0.5 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the silicone composition.
- the amount of water used in the emulsification may be such that the concentration of the nitrogen atom-containing organopolysiloxane is 10 to 80% by mass, and preferably 20 to 70% by mass.
- the above-mentioned emulsion can be obtained by a conventionally known method, and the above-mentioned silicone composition and an emulsifier are mixed, and this is mixed with a homomixer, a homogenizer, a colloid mill, a line mixer, a universal mixer (trade name), an ultramixer ( What is necessary is just to emulsify with an emulsifying machine, such as a brand name), a planetary mixer (brand name), a combination mix (brand name), and a three-roll mixer.
- the fiber treating agent of the present invention further includes, within a range that does not impair the object of the present invention, a fiber agent such as a wrinkle inhibitor, a flame retardant, an antistatic agent, a heat resistant agent, an antioxidant, an ultraviolet absorber, Components such as pigments, metal powder pigments, rheology control agents, curing accelerators, deodorants, and antibacterial agents can also be added.
- a fiber agent such as a wrinkle inhibitor, a flame retardant, an antistatic agent, a heat resistant agent, an antioxidant, an ultraviolet absorber, Components such as pigments, metal powder pigments, rheology control agents, curing accelerators, deodorants, and antibacterial agents can also be added.
- the fiber treating agent of the present invention when attached to the fiber, it can be attached to the fiber by dipping, spraying, roll coating, or the like.
- the amount of adhesion varies depending on the type of fiber and is not particularly limited.
- the component (A) or the component (B) in the silicone composition to be mixed with the fiber treating agent is mixed, the components (A) and (B) Generally, the total adhesion amount is in the range of 0.01 to 100% by mass of the fiber mass. Then, it may be dried by blowing with hot air or a heating furnace. Drying may be performed at 100 to 180 ° C. for 30 seconds to 5 minutes, although it varies depending on the type of fiber.
- the shape and shape of the fiber of the present invention are not limited, and are not limited to raw material shapes such as staples, filaments, tows, and yarns, and various processed forms such as woven fabric, knitted fabric, wadding, and nonwoven fabric. It is an object that can be treated by the treatment agent.
- the silicone composition of the present invention can be used for various purposes other than fiber treatment, such as paints, adhesives, sealants, inks, impregnating agents such as papers, surface treatments, and cosmetics. Can be used for At this time, an additive can be used as needed.
- additives include anti-wrinkling agents, flame retardants, antistatic agents, fiber agents such as heat-resistant agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, deodorants. Agents, antibacterial agents and the like. These additives may be used alone or in combination of two or more.
- 1 H-NMR is a value measured with a 400 MHz FT-NMR apparatus (manufactured by JEOL Ltd.) in a heavy chloroform solvent. It is a number average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) analysis using a developing solvent.
- a 30 mass% isopropanol solution a-1 of a copolymer (molecular weight: 15,000) represented by the following formula (A-1) was obtained.
- n is a number having the above-mentioned molecular weight.
- a 30 mass% isopropanol solution a-4 of a copolymer (molecular weight: 38,000) represented by the following formula (A-4) was obtained.
- n is a number having the above-mentioned molecular weight.
- Example 1 100 parts of a 30 mass% isopropanol solution a-1 of the copolymer represented by the formula (A-1) obtained in Synthesis Example 1 and 10 parts of a polyether-modified silicone represented by the following formula (B-1) are mixed, A silicone composition (1) was obtained.
- Example 2 100 parts of a 30 mass% isopropanol solution a-1 of the copolymer represented by the formula (A-1) obtained in Synthesis Example 1 and 10 parts of a polyether-modified silicone represented by the following formula (B-2) are mixed, A silicone composition (2) was obtained.
- Example 3 100 parts of a 30% by mass isopropanol solution a-2 of the copolymer represented by the formula (A-2) obtained in Synthesis Example 2 and 10 parts of the polyether-modified silicone represented by the formula (B-1) are mixed, A silicone composition (3) was obtained.
- Example 4 100 parts of a 30 mass% isopropanol solution a-3 of the copolymer represented by the formula (A-3) obtained in Synthesis Example 3 and 10 parts of the polyether-modified silicone represented by the formula (B-1) are mixed, A silicone composition (4) was obtained.
- Example 5 100 parts of a 30% by mass isopropanol solution a-4 of the copolymer represented by the formula (A-4) obtained in Synthesis Example 4 and 10 parts of the polyether-modified silicone represented by the formula (B-1) are mixed, A silicone composition (5) was obtained.
- Example 6 100 parts of a 30% by mass isopropanol solution a-1 of the copolymer represented by the formula (A-1) obtained in Synthesis Example 1 and 2 parts of lactic acid were mixed to obtain a silicone composition (6).
- Example 7 100 parts of a 30 mass% isopropanol solution a-1 of the copolymer represented by the formula (A-1) obtained in Synthesis Example 1 and 2 parts of acetic acid were mixed to obtain a silicone composition (7).
- Example 8 100 parts of a 30% by mass isopropanol solution a-3 of the copolymer represented by the formula (A-3) obtained in Synthesis Example 3 and 2 parts of lactic acid were mixed to obtain a silicone composition (8).
- Example 9 100 parts of a 30% by mass isopropanol solution a-1 of the copolymer represented by the formula (A-1) obtained in Synthesis Example 1, 5 parts of the polyether-modified silicone represented by the formula (B-1), and 2 parts of lactic acid was mixed to obtain a silicone composition (9).
- Example 10 100 parts of a 30 mass% isopropanol solution a-1 of the copolymer represented by the formula (A-1) obtained in Synthesis Example 1, 5 parts of the polyether-modified silicone represented by the above formula (B-1), and 2 parts of acetic acid was mixed to obtain a silicone composition (10).
- Example 11 100 parts of a 30 mass% isopropanol solution a-3 of the copolymer represented by the formula (A-3) obtained in Synthesis Example 3, 100 parts of the polyether-modified silicone represented by the above formula (B-1), and 2 parts of lactic acid was mixed to obtain a silicone composition (11).
- the total amount of the copolymer and the polyether-modified silicone in the composition was 10% by mass of the fiber mass), and the mixture was heated at 150 ° C. for 2 minutes. Thereafter, one drop (25 ⁇ L) of tap water was dropped on the treated cloth with a dropper, and the time (second) until the water drop was completely absorbed by the cloth was measured (water absorption before washing). Thereafter, the treated cloth was washed once by a washing machine by a method based on JIS L0217 103. One drop (25 ⁇ L) of tap water was dropped on the treated cloth with the dropper, and the time (second) until the water drop was completely absorbed by the cloth was measured (water absorption after washing). The results are shown in Tables 1 to 3.
- the silicone composition of the present invention has excellent water dispersibility and can impart excellent water absorption to the fiber surface. Furthermore, the fiber treatment agent using the silicone composition of the present invention has good durability, and the fiber surface after washing can maintain high water absorption.
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Abstract
Description
[1].
下記(A1)成分と、下記(B)成分及び/又は下記(C)成分を含有するシリコーン組成物。
(A1)下記一般式(1-1)で表される窒素原子含有オルガノポリシロキサンと、下記一般式(2-1)又は(2-2)で表されるポリオキシアルキレン基含有エポキシ化合物との反応生成物である、分子内にシロキサン基とポリオキシアルキレン基を有するコポリマー:100質量部、
(B)下記一般式(4)で表されるポリエーテル変性シリコーン:1~50質量部、
(C)有機酸:0.1~20質量部。
[2].
下記(A2)成分と、下記(B)成分及び/又は下記(C)成分を含有するシリコーン組成物。
(A2)下記一般式(1-2)又は(1-3)で表されるエポキシ基含有オルガノポリシロキサンと、下記一般式(2-3)で表されるポリオキシアルキレン基含有アミン化合物との反応生成物である、分子内にシロキサン基とポリオキシアルキレン基を有するコポリマー:100質量部、
(B)下記一般式(4)で表されるポリエーテル変性シリコーン:1~50質量部、
(C)有機酸:0.1~20質量部。
[3].
(B)成分において、式(4)のeが0~50の整数である[1]又は[2]に記載のシリコーン組成物。
[4].
[1]~[3]のいずれかに記載のシリコーン組成物を含有する繊維処理剤。
[5].
更に、(D)水を含む[4]に記載の繊維処理剤。
本発明のシリコーン組成物は、(A)ポリシロキサンとポリアルキレンオキシドの繰り返し単位からなるコポリマーと、(B)ポリエーテル変性シリコーン及び/又は(C)有機酸を含有するものである。
(A)成分のポリシロキサンとポリアルキレンオキシドの繰り返し単位からなるコポリマーとしては、下記に示す(A1)又は(A2)成分を用いる。
ここで、R10の炭素数1~10の2価炭化水素基としては、例えば、メチレン基、エチレン基、プロピレン基(トリメチレン基、メチルエチレン基)、ブチレン基(テトラメチレン基、メチルプロピレン基)、ヘキサメチレン基、オクタメチレン基等のアルキレン基、フェニレン基等のアリーレン基、これらの基の2種以上の組み合わせ(アルキレン・アリーレン基等)などが挙げられる。
また、R11は水素原子又は炭素数1~4の1価炭化水素基であり、炭素数1~4の1価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等のアルキル基などが挙げられる。
R3として、より好ましくはエチレン基、トリメチレン基、メチルエチレン基、-CH2CH2CH2-NH-CH2CH2-である。
aが0では柔軟剤として使用した際の繊維への風合い付与能力が乏しく、1,000より大きいと水への分散性が低下する。
なお、(C2H4O)b(C3H6O)cで表されるポリオキシアルキレン基は、ブロック構造であってもランダム構造であってもよい。
有機溶剤の使用量は特に制限はないが、(A1)成分のコポリマーを製造する場合、式(1-1)で表される窒素原子含有オルガノポリシロキサンと、式(2-1)又は(2-2)で表されるポリオキシアルキレン基含有エポキシ化合物との合計100質量部に対して10~1,000質量部が好ましく、20~500質量部が特に好ましい。
また、(A2)成分のコポリマーを製造する場合、式(1-2)又は(1-3)で表されるエポキシ基含有オルガノポリシロキサンと、式(2-3)で表されるポリオキシアルキレン基含有アミン化合物との合計100質量部に対して10~1,000質量部が好ましく、20~500質量部が特に好ましい。
(B)成分は、下記一般式(4)で表されるポリエーテル変性シリコーンである。(B)成分は1種単独で又は2種以上を適宜組み合わせて用いることができる。
なお、式(4)において、f=0のとき、R8のうち少なくとも1つがR7であり、また、本発明においては、式(4)中にR7を1~10個、特に1~5個有することが好ましい。
(C)成分は有機酸である。これは1種単独で又は2種以上を適宜組み合わせて用いることができる。
具体的には、モノカルボン酸、ジカルボン酸、ヒドロキシカルボン酸、芳香族カルボン酸及び酸性アミノ酸等が挙げられる。より具体的には、酢酸、プロピオン酸及びカプリル酸等のモノカルボン酸;マロン酸、コハク酸、グルタル酸、アジピン酸、マレイン酸及びフマル酸等のジカルボン酸;グリコール酸、乳酸、ヒドロキシアクリル酸、グリセリン酸、リンゴ酸、酒石酸及びクエン酸等のヒドロキシカルボン酸;安息香酸、サリチル酸及びフタル酸から選択される芳香族カルボン酸;グルタミン酸及びアスパラギン酸等の酸性アミノ酸が挙げられる。
溶剤としては、例えば、ジブチルエーテル、ジオキサン、THF等のエーテル系溶剤、アセトン、MEK等のケトン系溶剤、メタノール、エタノール、2-プロパノール、n-ブタノール、sec-ブタノール、2-エチル-1-ヘキサノール、2-メトキシエタノール、2-エトキシエタノール、2-ブトキシエタノール、エチレングリコール、ジエチレングルコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、2-メチル-1,2-プロパンジオール、1,5-ペンタンジオール、2-メチル-2,3-ブタンジオール、1,6-ヘキサンジオール、1,2-ヘキサンジオール、2,5-ヘキサンジオール、2-メチル-2,4-ペンタンジオール、2,3-ジメチル-2,3-ブタンジオール、2-エチル-1,6-ヘキサンジオール、1,2-オクタンジオール、1,2-デカンジオール、2,2,4-トリメチルペンタンジオール、2-ブチル-2-エチル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール等のアルコール系溶剤、トルエン、キシレン等の芳香族系溶剤が挙げられる。これらの溶剤は単独で用いてもよく、2種類以上を併用してもよい。
有機溶剤を配合する場合の使用量は特に制限はないが、上記シリコーン組成物100質量部に対して2,000~200,000質量部が好ましく、10,000~100,000質量部が特に好ましい。
添加剤としては、例えば、防しわ剤、難燃剤、帯電防止剤、耐熱剤等の繊維用薬剤、酸化防止剤、紫外線吸収剤、顔料、金属粉顔料、レオロジーコントロール剤、硬化促進剤、消臭剤、抗菌剤等が挙げられる。これらの添加剤は単独で用いてもよく、2種類以上を併用してもよい。
なお、下記の例において、部は質量部を示し、1H-NMRは、重クロロホルム溶媒中、400MHz FT-NMR装置(日本電子株式会社製)にて測定したものであり、分子量は、THFを展開溶媒としたゲルパーミエーションクロマトグラフィ(GPC)分析におけるポリスチレン換算の数平均分子量である。
温度計、撹拌装置、還流冷却器及び窒素ガス導入管のついたセパラブルフラスコに、下記式(X-1)で示されるアミノアルキル基含有オルガノポリシロキサン200g(アミノ基量0.13mоl)、下記式(Y-1)で示されるポリオキシアルキレン基含有エポキシ化合物23.4g(エポキシ基量0.13mоl)、及びイソプロパノール521.3gを仕込み、窒素ガスを導入した後に密閉して、80℃で4時間付加反応を行った。
1H-NMRによりエポキシ基が仕込みの99モル%以上消費されていることを確認した。
下記式(A-1)で示されるコポリマー(分子量15,000)の30質量%イソプロパノール溶液a-1を得た。
温度計、撹拌装置、還流冷却器及び窒素ガス導入管のついたセパラブルフラスコに、下記式(X-2)で示されるアミノアルキル基含有オルガノポリシロキサン111g(アミノ基量0.05mоl)、上記式(Y-1)で示されるポリオキシアルキレン基含有エポキシ化合物8.88g(エポキシ基量0.05mоl)、及びイソプロパノール280gを仕込み、窒素ガスを導入した後に密閉して、80℃で4時間付加反応を行った。
1H-NMRによりエポキシ基が仕込みの99モル%以上消費されていることを確認した。
下記式(A-2)で示されるコポリマー(分子量23,000)の30質量%イソプロパノール溶液a-2を得た。
温度計、撹拌装置、還流冷却器及び窒素ガス導入管のついたセパラブルフラスコに、上記式(X-2)で示されるアミノアルキル基含有オルガノポリシロキサン108g(アミノ基量0.05mоl)、下記式(Y-2)で示されるポリオキシアルキレン基含有エポキシ化合物12g(エポキシ基量0.05mоl)、及びイソプロパノール280gを仕込み、窒素ガスを導入した後に密閉して、80℃で4時間付加反応を行った。
1H-NMRによりエポキシ基が仕込みの99モル%以上消費されていることを確認した。
下記式(A-3)で示されるコポリマー(分子量27,000)の30質量%イソプロパノール溶液a-3を得た。
温度計、撹拌装置、還流冷却器及び窒素ガス導入管のついたセパラブルフラスコに、下記式(X-3)で示されるアミノアルキル基含有オルガノポリシロキサン110g(アミノ基量0.04mоl)、上記式(Y-2)で示されるポリオキシアルキレン基含有エポキシ化合物10g(エポキシ基量0.04mоl)、及びイソプロパノール280gを仕込み、窒素ガスを導入した後に密閉して、80℃で4時間付加反応を行った。
1H-NMRによりエポキシ基が仕込みの99モル%以上消費されていることを確認した。
下記式(A-4)で示されるコポリマー(分子量38,000)の30質量%イソプロパノール溶液a-4を得た。
特許第3859723号公報の実施例における表2、コポリマーAB-20-18の製造方法に倣い、下記式(Y-3)で示されるアミン化合物30.5g(アミノ基量0.06mоl)、イソプロパノール80.5gを温度計、撹拌装置、還流冷却器、滴下漏斗及び窒素ガス導入管のついたセパラブルフラスコに仕込み、混合した。混合液の温度を80℃に調整し、下記式(X-4)で示されるポリシロキサン50g(エポキシ基量0.05mоl)を滴下漏斗から滴下した。80℃で6時間の加熱撹拌後、1H-NMRによりエポキシ基が仕込みの99モル%以上消費されていることを確認し、シリコーン生成物a-5を得た。
a-5中ブロックコポリマーの構造式は、下記式(A-5)で示されるものと推定される(分子量11,000)。
合成例1で得られた式(A-1)で示されるコポリマーの30質量%イソプロパノール溶液a-1を100部、下記式(B-1)で示されるポリエーテル変性シリコーン10部を混合し、シリコーン組成物(1)を得た。
合成例1で得られた式(A-1)で示されるコポリマーの30質量%イソプロパノール溶液a-1を100部、下記式(B-2)で示されるポリエーテル変性シリコーン10部を混合し、シリコーン組成物(2)を得た。
合成例2で得られた式(A-2)で示されるコポリマーの30質量%イソプロパノール溶液a-2を100部、上記式(B-1)で示されるポリエーテル変性シリコーン10部を混合し、シリコーン組成物(3)を得た。
合成例3で得られた式(A-3)で示されるコポリマーの30質量%イソプロパノール溶液a-3を100部、上記式(B-1)で示されるポリエーテル変性シリコーン10部を混合し、シリコーン組成物(4)を得た。
合成例4で得られた式(A-4)で示されるコポリマーの30質量%イソプロパノール溶液a-4を100部、上記式(B-1)で示されるポリエーテル変性シリコーン10部を混合し、シリコーン組成物(5)を得た。
合成例1で得られた式(A-1)で示されるコポリマーの30質量%イソプロパノール溶液a-1を100部、乳酸2部を混合し、シリコーン組成物(6)を得た。
合成例1で得られた式(A-1)で示されるコポリマーの30質量%イソプロパノール溶液a-1を100部、酢酸2部を混合し、シリコーン組成物(7)を得た。
合成例3で得られた式(A-3)で示されるコポリマーの30質量%イソプロパノール溶液a-3を100部、乳酸2部を混合し、シリコーン組成物(8)を得た。
合成例1で得られた式(A-1)で示されるコポリマーの30質量%イソプロパノール溶液a-1を100部、上記式(B-1)で示されるポリエーテル変性シリコーン5部、乳酸2部を混合し、シリコーン組成物(9)を得た。
合成例1で得られた式(A-1)で示されるコポリマーの30質量%イソプロパノール溶液a-1を100部、上記式(B-1)で示されるポリエーテル変性シリコーン5部、酢酸2部を混合し、シリコーン組成物(10)を得た。
合成例3で得られた式(A-3)で示されるコポリマーの30質量%イソプロパノール溶液a-3を100部、上記式(B-1)で示されるポリエーテル変性シリコーン5部、乳酸2部を混合し、シリコーン組成物(11)を得た。
合成例5で得られたシリコーン生成物a-5を単独で使用した。
合成例1で得られた式(A-1)で示されるコポリマーの30質量%イソプロパノール溶液a-1を単独で使用した。
合成例1で得られた式(A-1)で示されるコポリマーの30質量%イソプロパノール溶液a-1を100部、式(B-1)で示されるポリエーテル変性シリコーン0.1部を混合し、シリコーン組成物(12)を得た。
合成例1で得られた式(A-1)で示されるコポリマーの30質量%イソプロパノール溶液a-1を100部、乳酸0.01部を混合し、シリコーン組成物(13)を得た。
合成例1で得られた式(A-1)で示されるコポリマーの30質量%イソプロパノール溶液a-1を100部、式(B-1)で示されるポリエーテル変性シリコーン0.1部、乳酸0.01部を混合し、シリコーン組成物(14)を得た。
合成例3で得られた式(A-3)で示されるコポリマーの30質量%イソプロパノール溶液a-3を100部、式(B-1)で示されるポリエーテル変性シリコーン0.1部、乳酸0.01部を混合し、シリコーン組成物(15)を得た。
1.水分散性
上記実施例及び比較例で得たシリコーン組成物(比較例1の場合はシリコーン生成物、比較例2の場合はコポリマーの30質量%イソプロパノール溶液、以下同じ)0.2gと、イオン交換水9.8gをガラス瓶に入れて振とうし、外観を確認、下記基準にて評価した。結果を表1~3に示す。
○:水にサンプルの分散が可能。
×:水にサンプルの分散が不可。
上記実施例で得たシリコーン組成物6.67gにイオン交換水193.33gを加えて撹拌し、試験液を調製した。また、上記比較例で得たシリコーン組成物6.67gにトルエン193.33gを加えて撹拌し、試験液を調製した。該試験液にポリエステル/綿ブロード布(65%/35%、谷頭商店社製)を1分間浸漬した後、絞り率10%の条件でロールを用いて絞り(試験液に配合されるシリコーン組成物中のコポリマー、又はポリエーテル変性シリコーンを配合する場合はコポリマーとポリエーテル変性シリコーンの合計の付着量として繊維質量の10質量%)、150℃で2分間加熱処理して柔軟性評価用の処理布を作製した。該処理布を三人のパネラーが手触りし、柔軟性を以下の基準により評価した。結果を表1~3に示す。
A:触り心地が非常に良好である。
B:触り心地が良好である。
C:触り心地が悪い。
上記実施例で得たシリコーン組成物6.67gにイオン交換水193.33gを加えて撹拌し、試験液を調製した。また、上記比較例で得たシリコーン組成物6.67gにトルエン193.33gを加えて撹拌し、試験液を調製した。該試験液にポリエステル/綿ブロード布(65%/35%、谷頭商店社製)を1分間浸漬した後、絞り率10%の条件でロールを用いて絞り(試験液に配合されるシリコーン組成物中のコポリマー、又はポリエーテル変性シリコーンを配合する場合はコポリマーとポリエーテル変性シリコーンの合計の付着量として繊維質量の10質量%)、150℃で2分間加熱処理した。その後、本処理布にスポイトで水道水を一滴(25μL)滴下し、水滴が布に完全に吸収されるまでの時間(秒)を測定した(洗濯前吸水性)。その後、本処理布を、JIS L0217 103に準拠した手法により、洗濯機による洗濯を一回行った。洗濯を行った処理布に対し、スポイトで水道水を一滴(25μL)滴下し、水滴が布に完全に吸収されるまでの時間(秒)を測定した(洗濯後吸水性)。結果を表1~3に示す。
上記実施例で得たシリコーン組成物6.67gにイオン交換水193.33gを加えて撹拌し、試験液を調製した。また、上記比較例で得たシリコーン組成物6.67gにトルエン193.33gを加えて撹拌し、試験液を調製した。該試験液にポリエステル/綿ブロード布(65%/35%、谷頭商店社製)を1分間浸漬した後、絞り率10%の条件でロールを用いて絞り(試験液に配合されるシリコーン組成物中のコポリマー、又はポリエーテル変性シリコーンを配合する場合はコポリマーとポリエーテル変性シリコーンの合計の付着量として繊維質量の10質量%)、150℃で2分間加熱処理した。その後、本処理布を、JIS L0217 103に準拠した手法により、洗濯機による洗濯を一回行った。洗濯一回後の繊維表面のシリコーン残存量を蛍光X線分析装置(Rigaku社製)にて測定し、洗濯を行っていない場合と比較し、残存率(%)を計算した。結果を表1~3に示す。
Claims (5)
- 下記(A1)成分と、下記(B)成分及び/又は下記(C)成分を含有するシリコーン組成物。
(A1)下記一般式(1-1)で表される窒素原子含有オルガノポリシロキサンと、下記一般式(2-1)又は(2-2)で表されるポリオキシアルキレン基含有エポキシ化合物との反応生成物である、分子内にシロキサン基とポリオキシアルキレン基を有するコポリマー:100質量部、
(B)下記一般式(4)で表されるポリエーテル変性シリコーン:1~50質量部、
(C)有機酸:0.1~20質量部。 - 下記(A2)成分と、下記(B)成分及び/又は下記(C)成分を含有するシリコーン組成物。
(A2)下記一般式(1-2)又は(1-3)で表されるエポキシ基含有オルガノポリシロキサンと、下記一般式(2-3)で表されるポリオキシアルキレン基含有アミン化合物との反応生成物である、分子内にシロキサン基とポリオキシアルキレン基を有するコポリマー:100質量部、
(B)下記一般式(4)で表されるポリエーテル変性シリコーン:1~50質量部、
(C)有機酸:0.1~20質量部。 - (B)成分において、式(4)のeが0~50の整数である請求項1又は2に記載のシリコーン組成物。
- 請求項1~3のいずれか1項に記載のシリコーン組成物を含有する繊維処理剤。
- 更に、(D)水を含む請求項4に記載の繊維処理剤。
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JP2014084398A (ja) | 2012-10-23 | 2014-05-12 | Shin Etsu Chem Co Ltd | 自己乳化性マイクロエマルション組成物及び繊維処理剤 |
WO2016166979A1 (ja) * | 2015-04-14 | 2016-10-20 | 東レ・ダウコーニング株式会社 | ポリエーテル-ポリシロキサンブロック共重合体組成物、それを含む界面活性剤、整泡剤、ポリウレタン発泡体形成組成物、化粧料およびその製造方法 |
JP2018016909A (ja) * | 2016-07-28 | 2018-02-01 | 信越化学工業株式会社 | 皮膜形成性シリコーンエマルション組成物及び繊維処理剤 |
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WO2022034829A1 (ja) * | 2020-08-11 | 2022-02-17 | 信越化学工業株式会社 | シリコーンエマルション組成物及び繊維処理剤 |
JP7332052B2 (ja) | 2020-08-11 | 2023-08-23 | 信越化学工業株式会社 | シリコーンエマルション組成物及び繊維処理剤 |
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TW202006070A (zh) | 2020-02-01 |
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